CN101868509A - Use of highly branched polymers in polymer dispersions for gloss colours - Google Patents

Use of highly branched polymers in polymer dispersions for gloss colours Download PDF

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CN101868509A
CN101868509A CN200880116779A CN200880116779A CN101868509A CN 101868509 A CN101868509 A CN 101868509A CN 200880116779 A CN200880116779 A CN 200880116779A CN 200880116779 A CN200880116779 A CN 200880116779A CN 101868509 A CN101868509 A CN 101868509A
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ester
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CN101868509B (en
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S·霍勒
B·布鲁赫曼
R·德尔施
D·舍恩菲尔德
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention relates to a method for producing coatings with increased gloss, aqueous coating agents for such a method, and the use of highly-branched polymers as additives for aqueous polymer dispersions for coating agents used to increase the gloss of coatings.

Description

Highly-branched polymers is used for the polymeric dispersions of gloss colorant
The present invention relates to prepare the method for the coating of glossiness with increase, relate to the water-borne coatings that is used for described method, and relating to the purposes of highly-branched polymers as the additive of the aqueous polymer dispersions that is used for coating, described coating produces the coating of the glossiness with increase.
Lacquer is divided three classes usually according to its reflecting power:
1. do not have wartwort, its mirror surface luster is that reflectivity is lower than 15%;
2. semi-gloss paint, its mirror surface luster is a reflectivity about 35% to 50%; And
3. high gloss paint, its mirror surface luster is that reflectivity is greater than 70%;
Be 60 ° photometry separately based on input angle.
Depend primarily on the glossiness of gained coating based on the quality of the not pigmented coating of aqueous polymer dispersions and specific pigmented coating.Therefore attempt improving glossiness by suitable additive always.Yet in many cases, these additives have and still demonstrate certain volatile shortcoming, and this VOC to the gained coating has detrimentally affect.
WO 00/29495 has described a kind of coating, and it comprises a kind of solvent, a kind of Synolac (vibrin) and a kind of star polymer.Described star polymer in the described coating is as the properties-correcting agent of the performance of improving described coating, and the described performance of improving for example reaches lower viscosity.Described star polymer comes from the multi-functional thiol of containing at least three ethylenic unsaturated terminal chains.
WO 01/96411 has described a kind of amphiphilic star-like polymkeric substance that has based on the nuclear of mercaptan, extends at least three polymeric arms from described nuclear, has also described the purposes that described star polymer is used for stabilized aqueous polymeric dispersions.
WO 2004/016700 has described a kind of copolymer dispersion based on water, and it can obtain by using at least a branch-shape polymer with alkene functional group to carry out copolymerization.The remarkable part of gained copolymer dispersion is to have improved block character.The document is not instructed and is added highly-branched polymers in hydrotropisms's polymeric dispersions so that water-borne coatings to be provided, and described coating can produce the coating of the glossiness with increase.
WO 2004/016701 has described a kind of water-based homopolymer or copolymer dispersion, and it can obtain by letex polymerization, and the branch-shape polymer that wherein uses a kind of alkenyl functional is as additive.Said composition can be used as the base-material of coating.There is not to disclose the purposes that it is used to increase glossiness.
WO 2004/037928 has described a kind of air dried aqueous resin composition, and it is made up of the functional hyperbranched polymer of a kind of lipid acid at air drying, a kind of non-amphipathic Synolac, a kind of siccative and a kind of stablizer.
WO 2005/003186 has described a kind of method for preparing aqueous polymer dispersions, and is described dispersion-based in the multipolymer that contains hydrophobicity allyl group, vinyl, toxilic acid or diene monomers, is aggregated under the existence of at least a branch-shape polymer to carry out.Branch-shape polymer in this system makes even the strong-hydrophobicity monomer that can use water solubility to be lower than 0.001g/l carries out letex polymerization.Do not put down in writing described branch-shape polymer is used as the additive of polymeric dispersions so that the coating of the coating that can generate the glossiness with increase to be provided.
EP 1006165A2 has described a kind of coating composition that contains vinyl polymer, and described polymkeric substance has carbon siloxanes (carbosiloxane) dendrimers side group.These groups carry out free-radical polymerized being introduced into by the carbon siloxanes dendrimers with vinyl functional.This coating composition is used for building industry, buildings, automobile etc.Coating is weather-proof, waterproof and freeze proof, and demonstrates good gloss retentivity and water repellency.
K.Manczyk, P.Szewczyk be at Prog.Org.Coat.2002, and 44, highly branched high-solid level Synolac has been described among the 99-109.These resins can be based on star structure and dissaving structure.Along with the degree of branching increases, the drying of these Synolac is accelerated.Except other functions, also reported glossiness.But the document does not show the suitability of hyperbranched polymer as the special additive that is used to improve glossiness.One piece of similar disclosure is E.Bat, and G.G ü nd ü z, D.Kisak ü rek, and I.M.Akhmedoc be at Prog.Org.Coat.2006,55, and the article among the 330-336.
An object of the present invention is to provide the aqueous polymer dispersions of the lacquer of the glossiness that is used for having increase.This dispersion especially is applied to increase the glossiness based on the gloss paint of acrylate dispersoid.
Surprisingly, find that this purpose is by using highly branched polymkeric substance to realize at the aqueous polymer dispersions that is used for coating.
Therefore the present invention at first provides the method for preparing the coating of the glossiness with increase by a kind of water-borne coatings of coating on base material, and described water-borne coatings comprises a kind of aqueous polymer dispersions PD) and a kind of highly-branched polymers.
The present invention also provides the coating of waterborne compositions form, and it comprises:
-at least a with undefined dispersion, it comprises a kind of highly branched polymkeric substance as additive,
If-suitable, at least a mineral filler and/or mineral dye,
-conventional auxiliary agent and
-add to the water of 100 weight %.
The present invention also provides a kind of to be increased based on aqueous polymer dispersions PD by adding at least a highly-branched polymers) the method for glossiness of coating, described aqueous polymer dispersions can pass through at least a α, β-ethylenically unsaturated monomers M) free-radical emulsion polymerization obtain.
To polymeric dispersions PD) in add highly branched polymkeric substance and can be used to prepare PD) letex polymerization before and/or among and/or carry out afterwards.The interpolation of carrying out after letex polymerization also comprises the product that comprise a kind of emulsion polymer of interpolation as the part of preparation, and described emulsion polymer is based at least a α, β-ethylenically unsaturated monomers M).For this reason, at least a as highly branched polymkeric substance that give a definition can be used as in the additive adding lacquer.Therefore the present invention also provides at least a highly branched polymkeric substance as the additive of the product purposes with the glossiness that increases coating prepared therefrom, described product comprises a kind of based at least a as α that gives a definition, β-ethylenically unsaturated monomers M) emulsion polymer.
The present invention also provides as the highly branched polymkeric substance of giving a definition as the additive of the water-borne coatings purposes with the glossiness that increases coating prepared therefrom, and described water-borne coatings comprises a kind of aqueous emulsion polymer PD).
The present invention also provides a kind of aqueous polymer dispersions PD) as the purposes of a kind of component in transparent varnish and the high gloss paint, described aqueous polymer dispersions PD) comprise a kind of highly branched polymkeric substance as additive.
The glossiness of lacquer can be measured by DIN 67530.The slit of lacquer by wide 240 μ m is applied on the sheet glass and drying at room temperature 72 hours.With the reflexometer of specimen insertion through calibration, use the input angle of determining, write down reflection or scattering and the degree of back light.The reflexometer numerical value of measuring is measure (this value is high more, and glossiness is high more) of glossiness.
The glossiness of semi-gloss paint preferably in the time of 60 ° greater than 15.Based on the glossiness of the high gloss paint of coating of the present invention preferably 20 ° the time greater than 60.The glossiness of high gloss paint preferably in the time of 60 ° greater than 80.
The polymeric dispersions PD that uses among the present invention) comprise preferred 0.1 to 15 weight %, the more preferably at least a highly branched polymkeric substance of 0.5 to 10 weight % is based on the gross weight meter of described polymeric dispersions.The amount of described highly branched polymkeric substance is usually in the scope of for example 1 weight % to 5 weight %.
The purposes of highly-branched polymers of the present invention has at least a following advantage:
-increase the glossiness of coating (lacquer), especially based on the gloss paint of acrylate dispersoid,
-used the highly-branched polymers and the highly compatible of multiple dispersion,
-avoid using the additive of the VOC content that increases dispersion at least in part.
According to the present invention to polymeric dispersions PD) in add at least a highly-branched polymers.Phrase " highly-branched polymers " is often referred to the polymkeric substance that is characterized as highly branched structure and high functionality in the present invention.General Definition for highly-branched polymers, also can be referring to P.J.Flory, J.Am.Chem.Soc.1952,74,2718 and H.Frey et al., Chem.Eur.J.2000,6, No.14,2499 (definition of " hyperbranched polymer " that the implication when wherein they are mentioned and this paper select is different).
Highly-branched polymers implication in the present invention comprises star polymer, dendrimers, dendrimer (arborol), and different highly-branched polymers, for example hyperbranched polymer particularly.
Star polymer is wherein three or many polymkeric substance that chain extends out from a center.This center can be single atom or atomic group.
The structure of dendrimers derives from star polymer, but has carried out star-branched from every independent chain.Dendrimers is obtained by continuous multiple reaction sequence by small molecules, and described reaction sequence produces more branch, has functional group separately at the ramose end, and described functional group is re-used as the starting point of further branching.Therefore the number of monomer end group is index with each reactions steps increases, and finally forms tree structure, and it is a spheric under perfect condition.A feature of dendrimers is reactions steps (generation) number that is carried out during it synthesizes.Because dendrimers is constructed (under perfect condition, all branches comprise the monomeric unit of identical number) uniformly, it is monodispersed substantially, and promptly it has definite molar mass usually.
Uniform highly-branched polymers is called as dendrimers hereinafter equally on molecule and the structure.
" hyperbranched polymer " in the context of the invention is molecule and structure on all uneven highly-branched polymers different with above-mentioned dendrimers.They have length and branching with and molar mass distribution (polymolecularity) on the side chain and/or the side branch of difference to some extent.
Highly-branched polymers of the present invention preferably has 10% to 100%, more preferably 10% to 90%, more especially 10% to 80% the per molecule degree of branching (DB).Degree of branching DB is defined as
DB (%)=(T+Z)/(T+Z+L) * 100, wherein
T is the mean number of the terminal monomeric unit that connects,
Z is the mean number of formation ramose monomeric unit,
L is the mean number of the monomeric unit of straight chain connection.
Dendrimers has at least 99% usually, 99.9% to 100% degree of branching DB especially.
Hyperbranched polymer preferably has 10% to 95%, more preferably 25% to 90%, 30% to 80% degree of branching DB more especially.
In order to obtain favourable gloss character, not only can utilization structure and molecule on dendrimers uniformly, can also use hyperbranched polymer.But the preparation of hyperbranched polymer is easier and more economical than dendrimers usually.Therefore; the preparation of for example single dispersion dendrimers is complicated; this is because in each Connection Step; need to introduce blocking group again with its removal; and before each new growth phase begins; need carry out a large amount of washing operations, the reason that Here it is dendrimers can only be prepared in laboratory scale usually.The molecular weight distribution of hyperbranched polymer also can be to producing favourable influence with its viscometric properties that carries out the dispersion of modification.Hyperbranched polymer also has more flexible structure than dendrimers.
The material that is suitable as highly-branched polymers is those materials that can obtain by polycondensation, addition polymerization or the addition polymerization of ethylenically unsaturated compounds normally.Preferred polycondensate.The repetition chemical reaction that polycondensation indicating function compound and suitable reactive compounds carry out, and remove low-molecular weight compound for example water, ethanol, HCl etc.The repetition chemical reaction that addition polymerization indicating function compound and suitable reactive compounds carry out and do not remove low-molecular weight compound.
Suitable use contains the polymkeric substance of the functional group that is preferably selected from following group: ether, ester group, carbonate group, amino, amide group, carbamate groups and urea groups.
As polymkeric substance, can use polycarbonate, polyester, polyethers, polyurethane(s), polyureas, polyamine and polymeric amide more especially, with and hybrid form, for example poly-(Semicarbazido manthanoate), poly-(ether amine), poly-(ester carbonic ether), poly-(ether carbonate), poly-(ether-ether), poly-(ether-ether carbonic ether) etc.
Preferred hyperbranched polymer is based on for example hyperbranched polymer of esteramides, amide amine, ester carbonic ether, ether carbonate, ether-ether, ether-ether carbonic ether, Semicarbazido manthanoate etc. of ether, amine, ester, carbonic ether, acid amides and their hybrid form.
As hyperbranched polymer, can use hyperbranched polycarbonates, hyperbranched poly (ether carbonate), hyperbranched poly (ether-ether), hyperbranched poly (ether-ether carbonic ether), hyper-branched polyester, hyperbranched polyether, hyperbranched poly carbamate, hyperbranched poly (Semicarbazido manthanoate), hyperbranched polyureas, hyperbranched polyamine, ultrabranching polyamide, hyperbranched poly (ether amine), hyperbranched poly (ester amine), hyperbranched poly (ether acid amides), hyperbranched poly (esteramides) more especially, and the mixture of these materials.A kind of hyperbranched polymer of particular form is a hyperbranched polycarbonates.The hyperbranched polymer of another kind of particular form is the hyperbranched polymer of nitrogen atom, especially polyurethane(s), polyureas, polyamine, polymeric amide, poly-(esteramides) and poly-(ester amine).
As highly-branched polymers, preferred use hyperbranched polycarbonates, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether), or contain at least a hyperbranched polymer mixture in hyperbranched polycarbonates, poly-(ether carbonate), poly-(the ester carbonic ether) or poly-(ether-ether carbonic ether).
The hyperbranched polymer that the present invention be fit to use with and preparation method thereof in following document, be described, these documents are all included the application by reference in.
Highly branched, the especially hyperbranched polycarbonate of-WO 2005/026234,
The hyper-branched polyester of-WO 01/46296, DE 101 63 163, DE 102 19 508 or DE 102 40 817,
The hyperbranched polyether of-WO 03/062306, WO 00/56802, DE 102 11 664 or DE 199 47 631,
The hyperbranched polymer of the nitrogen atom of-WO 2006/087227 (especially polyurethane(s), polyureas, polymeric amide, poly-(esteramides), poly-(ether acid amides),
The hyperbranched poly carbamate of-WO 97/02304 or DE 199 04 444,
The hyperbranched poly of-WO 97/02304 or DE 199 04 444 (Semicarbazido manthanoate),
The hyperbranched polyureas of-WO 03/066702, WO 2005/044897 and WO 2005/075541,
The hyperbranched amido polymer of-WO 2005/007726, especially poly-(ester amine),
The hyperbranched poly of-WO 99/16810 or EP 1 036 106 (esteramides),
The ultrabranching polyamide of-WO 2006/018125,
The hyperbranched poly of-WO 2006/089940 (ester carbonic ether).
Preferred polymkeric substance is weight-average molecular weight M wAbout 500 to 500000, preferred 750 to 200000, be more particularly 1000 to 100000 polymkeric substance.Molecular weight can by gel permeation chromatography with standard substance for example polymethylmethacrylate measure.
In the context of the invention, statement " alkyl " comprises straight chain and branched alkyl group.Suitable short-chain alkyl group for example is straight or branched C 1-C 7Alkyl, preferred C 1-C 6Alkyl, more preferably C 1-C 4Alkyl.It is more particularly including methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the 2-butyl, sec-butyl, the tertiary butyl, n-pentyl, the 2-amyl group, the 2-methyl butyl, the 3-methyl butyl, 1, the 2-dimethyl propyl, 1, the 1-dimethyl propyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, n-hexyl, the 2-hexyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 3-dimethylbutyl, 1, the 1-dimethylbutyl, 2, the 2-dimethylbutyl, 3, the 3-dimethylbutyl, 1,1,2-trimethylammonium propyl group, 1,2,2-trimethylammonium propyl group, the 1-ethyl-butyl, the 2-ethyl-butyl, 1-ethyl-2-methyl-propyl, n-heptyl, the 2-heptyl, the 3-heptyl, the 2-ethyl pentyl group, 1-propyl group butyl etc.
Suitable long-chain C 8-C 30Alkyl is the straight or branched alkyl.It is preferably the alkyl group of substantially linear, its also be present in natural or synthetic fatty acid and Fatty Alcohol(C12-C14 and C12-C18) and oxo alcohol (oxo-process alcohol) in.It for example comprises n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base etc.Statement " alkyl " comprises unsubstituted and substituted alkyl group.
The explanation of abovementioned alkyl also is applicable to the moieties of arylalkyl.The preferred aryl groups alkyl group is phenmethyl and styroyl.
In the context of the invention, C 8-C 32Thiazolinyl is represented straight chain and branched-chain alkenyl, and it can be single unsaturated, two unsaturated or polyunsaturated.Preferred C 10-C 20Thiazolinyl.The statement " thiazolinyl " comprise unsubstituted and substituted alkenyl group, its also be present in natural or synthetic fatty acid and Fatty Alcohol(C12-C14 and C12-C18) and oxo alcohol in.It is more particularly including octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base, vaccenic acid base, 19 carbene bases, inferior oil base (linolyl), flax base (linolenyl), 9,11,13-18 carbon trialkenyl and oil base (9-vaccenic acid base).
Statement " alkylidene group " represents to have straight or branched alkane two groups of 1 to 7 carbon atom, for example methylene radical, ethylene, trimethylene etc. in the present invention.
Cycloalkyl is preferably represented C 4-C 8Cycloalkyl, for example cyclobutyl, cyclopentyl, cyclohexyl, suberyl or ring octyl group.
Statement " aryl " comprises monocycle or polynuclear aromatics base in the present invention, and it can not be substituted or be substituted.Statement " aryl " preferably represent phenyl, tolyl, xylyl,
Figure GPA00001139222000071
Base, duryl, naphthyl, fluorenyl, anthryl, phenanthryl or naphthyl, more preferably phenyl or naphthyl, these aryl can have 1,2,3,4 or 5, preferred 1,2 or 3 substituting group usually under substituted situation.
More be particularly suitable for being used for the synthetic hyperbranched polymer that is applicable to the inventive method for being called as AB xMonomeric material.These monomers have two kinds of different functional group A and B, and this functional group can react to each other to form and connect.Only there is one in A functional group in each molecule, that B functional group exists is two or more (AB for example 2Or AB 3Monomer).AB xMonomer can side chain form included in hyperbranched polymer fully; It can be included into as end group, and therefore still has x free B group; It also can be used as the linear group with (x-1) individual free group and is included into.The hyperbranched polymer that is obtained has more or less B group, and described B group is positioned at end or as side group, depends on the polymerization degree.Further details is referring to for example Journal ofMolecular Science, Rev.Macromol.Chem.Phys., C37 (3), 555-579 (1997).
Except the group of acquisition in the dissaving structure synthetic (carbonate group during the synthesis of super branched polycarbonate for example; Carbamate during the synthesis of super branched polyurethane(s) and/or urea groups, and other groups that obtain by the reaction of isocyanate groups; Amide groups during the synthesis of super branched polymeric amide etc.) outside, the hyperbranched polymer that the present invention uses preferably also contains at least four other functional groups.Maximum numbers of these functional groups are inessential usually.But under many circumstances, it is no more than 100.The number of functional group is preferably 4 to 100, and especially 5 to 80, more particularly 6 to 50.
Other functional end-groups in the hyperbranched polymer that the present invention uses for example are independently from each other-OC (=O) OR ,-COOH ,-COOR ,-CONH 2,-CONHR ,-OH ,-NH 2,-NHR and-SO 3H.Terminal for OH, COOH and/or ROC (=O) hyperbranched polymer of O-group is proved to be particularly advantageous.
Hyperbranched polycarbonates
Be applicable to that the hyperbranched polycarbonates that increases glossiness can prepare by for example following steps:
A) make at least a general formula R aOC (=O) OR bOrganic carbonate (A) and at least a Fatty Alcohol(C12-C14 and C12-C18) (B) reaction that contains at least 3 OH groups, and cancellation alcohol R aOH and R bOH obtains one or more condensation products (K), R aAnd R bBe selected from straight or branched alkyl, arylalkyl, cycloalkyl and aromatic yl group independently of one another, R aAnd R bAlso can with group-OC that they connected (=O) O-is as cyclic carbonate,
B) condensation product (K) carries out the hyperbranched polycarbonates that intermolecular reaction generates high functionality,
The ratio of OH group and carbonic ether is selected as making condensation product (K) on average to contain a carbonate group and more than an OH group in the reaction mixture, perhaps contains an OH group and more than a carbonate group.Radicals R aAnd R bCan have identical or different definition.In a concrete scheme, R aAnd R bHas identical definition.Preferred R aAnd R bBe selected from C 1-C 20Alkyl, C 5-C 7Cycloalkyl, C 6-C 10Aryl and C 6-C 10Aryl-C 1-C 20Alkyl, as defined above.R aAnd R bAlso can be jointly as C 2-C 6Alkylidene group.Preferred especially R aAnd R bBe selected from the C of straight chain and side chain 1-C 5Alkyl, as above definition.
Dialkyl carbonate or diaryl carbonate can be by for example prepared in reaction of Fatty Alcohol(C12-C14 and C12-C18), fragrant Fatty Alcohol(C12-C14 and C12-C18) (araliphatic alcohol) or aromatic alcohol, preferred monohydroxy-alcohol and phosgene.In addition, its also can be by alcohol or phenol by CO at precious metal, oxygen or NO xExistence under oxidative carbonylation and prepare.About the preparation method of diaryl carbonate or dialkyl carbonate, also can be referring to Ullmann ' s Encyclopedia of Industrial Chemistry, 6 ThEdition, 2000Electronic Release, Wiley-VCH.
The example of suitable carbonic ether comprises aliphatics or aromatic carbonate, ethylene carbonate, 1 for example, 2-Texacar PC or 1, the two dodecyl esters of 3-Texacar PC, diphenyl carbonate, carboxylol ester, carbonic acid bis-xylene ester, carbonic acid dinaphthyl ester, carbonic acid ethyl phenyl ester, dimethyl benzyl, methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, carbonic acid diisobutyl ester, diamyl carbonate, carbonic acid dihexyl, carbonic acid two cyclohexyls, carbonic acid two heptyl esters, carbonic acid dioctyl ester, carbonic acid didecyl ester and carbonic acid.
The preferred aliphatic acid ester carbonate that uses more especially wherein contains the aliphatic acid ester carbonate of 1 to 5 atom in the group, for example methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or carbonic acid diisobutyl ester.
Organic carbonate contains the Fatty Alcohol(C12-C14 and C12-C18) (B) of at least 3 OH groups or mixture reaction of different alcohol with two or more with at least a.
Examples for compounds with at least three OH groups is glycerol, Pehanorm, trimethylolethane, TriMethylolPropane(TMP), 1,2,4-trihydroxybutane, three (methylol) amine, triethanolamine, tripropanolamine, tetramethylolmethane, two (TriMethylolPropane(TMP)s), two (tetramethylolmethanes), Glycerol dimer, triglycerin or low Polyglycerine, perhaps be for example glucose of sugar, have three or high functionality and based on having three or the Aethoxy Sklerol of pure and mild oxyethane, propylene oxide or the butylene oxide ring of high functionality more more, or polyesterols.Preferred especially glycerol, trimethylolethane, TriMethylolPropane(TMP), 1,2,4-trihydroxybutane, tetramethylolmethane, with and based on the Aethoxy Sklerol of oxyethane or propylene oxide.
These polyfunctional alcohols also can be used in the mixture of difunctional alcohol (B '), and condition is that the average OH functionality of used all alcohol is higher than 2.Example with suitable compound of two OH groups comprises ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol and 1, ammediol, dipropylene glycol, tripropylene glycol, neopentyl alcohol, 1,2-butyleneglycol, 1,3 butylene glycol and 1,4-butyleneglycol, 1,2-pentanediol, 1,3-pentanediol and 1,5-pentanediol, hexylene glycol, ring pentanediol, cyclohexanediol, cyclohexanedimethanol, and dual functional Aethoxy Sklerol or polyesterols.
The reaction of carbonic ether and alcohol or alcohol mixture generates and is used for high functionality hyperbranched polycarbonates of the present invention and from the alcohol or the phenol of carbonic ether molecule cancellation simple function.
After this reaction, use hydroxyl and/or carbonate group end-blocking by the high functionality hyperbranched polycarbonates that described method generates, promptly do not carry out further modification.It can easily be dissolved in multiple solvent, and for example water is pure as methyl alcohol, ethanol, butanols, alcohol/water mixture, acetone, 2-butanone, ethyl acetate, butylacetate, acetate methoxyl group propyl ester, acetate methoxyl group ethyl ester, tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, ethylene carbonate or Texacar PC.
The high functionality polycarbonate means in the context of the invention and also contains endways except the carbonate group that forms polymer backbone or at least four of side chain, preferred at least eight functional groups.Described functional group is carbonate group and/or OH group.Usually, the number of end or side chain functionalities does not have the upper limit; But the product with very many functional groups may demonstrate undesired character, for example high viscosity or low solubility.High functionality polycarbonate of the present invention has usually and is no more than 500 ends or side chain functionalities, preferably is no more than 100, more especially is no more than 50 ends or side chain functionalities.
For preparing described high functionality polycarbonate, the ratio that must will contain the compound of OH and carbonic ether is set at that the simplest condensation product (hereinafter being called condensation product (K)) that makes gained on average contains a carbonate group and more than an OH group or contain an OH group and more than a carbonate group.The simple structure of the condensation product (K) of carbonic ether (A) and glycol or polyvalent alcohol (B) is for arranging XY nOr YX n, X is a carbonate group, and Y is a hydroxyl, and n is generally 1 to 6, preferred 1 to 4, more preferably 1 to 3 integer.Reactive group is generated as separate base, is called " focus group " hereinafter.
By carbonic ether and the dibasic alcohol the simplest condensation product of preparation (K) time, reaction ratio is 1: 1, obtains the molecule of average out to XY type.When preparing condensation product (K) with 1: 1 reaction ratio, obtain average out to XY by carbonic ether and trivalent alcohol 2The molecule of type.When preparing condensation product (K) with 1: 1 reaction ratio, obtain average out to XY by carbonic ether and tetravalent alcohol 3The molecule of type.Condensation product (K) also can for example be prepared with 2: 1 reaction ratio of mol ratio by carbonic ether and trivalent alcohol.Obtain average out to X this moment 2The molecule of Y type, focus group are the OH group.When for example two carbonic ethers of glycol add in the component with difunctional compound in addition, cause chain extension.The same average out to XY that obtains 2The molecule of type, focus group are carbonate group.According to the present invention, the simplest condensation product (K) carries out intermolecular reaction and forms high functionality polycondensation product (P).The reaction that generates condensation product (K) and polycondensation product (P) takes place in body or solution under 0 to 250 ℃, preferred 60 to 160 ℃ temperature usually.In this case, can use usually each reactant is any solvent of inert.Preferably with an organic solvent, for example decane, dodecane, benzene, toluene, chlorobenzene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or solvent naphtha.
In a preferred embodiment, described condensation reaction is carried out in body.Can remove the simple function alcohol roh or the phenol that discharge in the reaction from molecular balance, to add fast response, this removes by the distillation mode and is undertaken, and carries out if be suitably under the pressure of reduction.
If use distillation to remove, then preferably use usually and in reaction, emit the carbonic ether that boiling point is lower than 140 ℃ alcohol roh.
In order to add fast response, can also add catalyzer or catalyst mixture.Appropriate catalyst is the compound of catalytic esterification or transesterification reaction, for example alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, the above-claimed cpd of preferred sodium, potassium or caesium, tertiary amine, guanidine, ammonium compound phosphonium compounds, organoaluminum, organotin, organic zinc, organic titanium, organic zirconium or bismuth organic compound, and the catalyzer that is known as double metal cyanide (DMC) class catalyzer are described in for example DE 10138216 or DE 10147712.
Preferred potassium hydroxide, salt of wormwood, the saleratus of using, diazabicyclo octane (DABCO), diazabicyclo-nonene (DBN), diazabicyclo undecylene (DBU), imidazoles is imidazoles, 1-Methylimidazole or 1,2 dimethylimidazole for example, four butanols titaniums, titanium tetraisopropylate, Dibutyltin oxide, dibutyl tin dilaurate, two stannous octoates, methyl ethyl diketone zirconium, or the mixture of these materials.
Catalyzer adds with the amount of 50 to 10000 ppm by weight, preferred 100 to 5000 ppm by weight usually, and described amount is based on the amount meter of used alcohol or alcohol mixture.
Can also be by the interpolation appropriate catalyst and/or by selecting suitable temperature to control intermolecular polycondensation.In addition, the molecular-weight average of polymkeric substance (P) can be regulated by the composition and the residence time of starting ingredient.
Condensation product (K) and polycondensation product (P) prepare at elevated temperatures, and it is at room temperature stable in a long time usually.
According to the character of condensation product (K), condensation reaction can produce the polycondensation product (P) with different structure, and it has side chain but does not have crosslinked.In addition, polycondensation product (P) contains a carbonic ether focus group and ideally more than two OH groups or contain an OH focus group and more than two carbonate groups.The number of reactive group depends on the character and the degree of polycondensation of employed condensation product (K).For example, condensation product (K) thus also can react and form two kinds of different condensation products (P) by three intermolecular polycondensations.
In order to stop the intermolecular condensation reaction, multiple feasible method is arranged.For example temperature can be reduced to reaction stops and the temperature of product (K) or condensation product (P) shelf-stable.
In another embodiment, in case the intermolecular reaction of condensation product (K) generates the polycondensation product (P) with required degree of polycondensation, promptly have and to come stopped reaction with the product of the group of the focus radical reaction of (P) by adding in product (P).For example, for carbonic ether focus group, for example can add monoamine, diamines or polyamines.For hydroxyl focus group, can in product (P), add for example monoisocyanates, vulcabond or polyisocyanates, contain the compound of epoxide group, or can with the acid derivative of OH radical reaction.
High functionality polycarbonate of the present invention usually under the pressure of 0.1mbar to 20bar, preferred 1mbar to 5bar intermittently, prepare in the reactor of semi-batch or operate continuously or the cascade reactor.
If by above-mentioned reaction conditions setting and---suitable---selection by suitable solvent, product can be further processed after preparation and purifying separately not.
In another preferred embodiment, described polycarbonate can not only contain the functional group that has obtained by reaction, also contains other functional groups.In this case, functionalized can be in the process that molecular weight increases or thereafter, be to carry out after actual polycondensation finishes.
If before molecular weight increases or during add the component that except hydroxyl or carbonate group, also contains other functional groups or sense element, then obtain to have stochastic distribution remove that carbonate group is rolled into a ball and hydroxyl the carbonate polymer of functionality.
This effect can for example realize that by add the compound that also contains other functional groups or sense element except hydroxyl, carbonate group or formamyl in polycondensation process described other functional groups or sense element be sulfydryl, primary amino, secondary amino group or uncle's amino, ether, carboxylic acid derivative, sulfonic acid, phosphonate derivative, aryl or chain alkyl for example.In order to carry out modification with carbamate groups, can for example use product, 4-hydroxy piperidine, 1-hydroxyethyl piperazine, diethanolamine, dipropanolamine, diisopropanolamine (DIPA), three (methylol) aminomethane, three (hydroxyethyl) aminomethane, 1, propylene diamine, hexamethylene-diamine or the isophorone diamine of the more high alkoxy degree of thanomin, Propanolamine, Yi Bingchunan, 2-(fourth amino) ethanol, 2-(hexamethylene amino) ethanol, 2-amino-1-butanols, 2-(2 '-amino ethoxy) ethanol or ammonia.
In order to use sulfydryl to carry out modification, can for example use mercaptoethanol.Uncle's amino can be by for example introducing N methyldiethanol amine, N-methyl dipropanolamine or N, N-dimethylethanolamine and generating.Ether can by for example in condensation course, introduce have two or more the Aethoxy Sklerol of high functionality generate.Can introduce chain alkyl with the reaction of long-chain alkane glycol; Generate the polycarbonate that contains alkyl, aryl and carbamate groups with the reaction of two alkyl isocyanates or two aryl isocyanates.
Ensuing functionalized high functionality hyperbranched polycarbonates by gained and suitable functionalized reagent's reaction realizes that described suitable functionalized reagent can react with the OH and/or the carbonate group of polycarbonate.
Containing the molecule that the high functionality hyperbranched polycarbonates of hydroxyl can be for example contains acidic group or isocyanate groups by adding is modified.The polycarbonate that contains acidic group for example can be by obtaining with the compound reaction that contains anhydride group.
In addition, the high functionality polycarbonate of hydroxyl also can be by being converted into high functionality polycarbonate-polyether glycol with oxirane---for example oxyethane, propylene oxide or butylene oxide ring---reaction.
Another important advance of the inventive method is its economy.Form the reaction of condensation product (K) or polycondensation product (P) and (K) or (P) all can carry out in a reaction unit with the reaction of other functional groups or element generation polycarbonate, this all has superiority technically and economically.
Hyper-branched polyester
As hyper-branched polyester, preferably use A 2B xThe hyper-branched polyester of type.Preferred especially A 2B 3The hyper-branched polyester of type.With AB 2The hyper-branched polyester of type is compared, these A 2B 3The polyester of type has the lower structure of rigidity.Therefore not preferred AB 2The hyper-branched polyester of type.
Be applicable to that the hyper-branched polyester that increases glossiness can be by at least a aliphatics, annular aliphatic, aromatic-aliphatic or aromatic dicarboxylic acid (A 2) or derivatives thereof and following substances reaction acquisition:
A) aliphatics of at least a trifunctional at least, annular aliphatic, aromatic-aliphatic or aromatic alcohols (B 3), or
B) at least a divalence aliphatics, annular aliphatic, aromatic-aliphatic or aromatic alcohols (B 2) and at least a x valency aliphatics, annular aliphatic, aromatic-aliphatic or the aromatic alcohols (C that contains more than two OH groups x), x be greater than 2, preferred 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4 number, more especially 3,
Perhaps by at least a aliphatics, annular aliphatic, aromatic-aliphatic or the aromatic carboxylic acid (D that contains more than two acidic groups y) reaction of or derivatives thereof and following compound obtains, wherein y be greater than 2, preferred 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4 number, more especially 3, described compound is:
C) at least a at least two functional aliphatics, annular aliphatic, aromatic-aliphatic or aromatic alcohols (B 3), or
D) at least a divalence aliphatics, annular aliphatic, aromatic-aliphatic or aromatic alcohols (B 2) and at least a x valency aliphatics, annular aliphatic, aromatic-aliphatic or the aromatic alcohols (C that contains more than two OH groups x), x be greater than 2, preferred 3 to 8, more preferably 3 to 6, extremely preferred 3 to 4 number, more especially 3,
E) if be suitably under the existence of other functionalized unit E, and
F) optionally next react with monocarboxylic acid F,
It is 5: 1 to 1: 5 that the ratio of the reactive group in the reaction mixture is chosen as the mol ratio that makes OH group and carboxyl or derivatives thereof, preferred 4: 1 to 1: 4, and more preferably 3: 1 to 1: 3, extremely preferred 2: 1 to 1: 2.
Hyper-branched polyester mean in the present invention contain hydroxyl and carboxyl and structurally with molecule on all uneven non-crosslinked polyester.Non-crosslinked in this specification sheets means the degree of crosslinking of existence less than 15 weight %, and preferably less than 10 weight %, its insoluble umber by polymkeric substance is determined.The insoluble umber of polymkeric substance is that tetrahydrofuran (THF) or hexafluoroisopropanol carry out extraction in four hours and determine by using with the used identical solvent of gel permeation chromatography, depend on which kind of solvent has better dissolving power to polymkeric substance, be extracted in the Soxhlet equipment and carry out, again residuum is dried to constant weight, and the weight of weighing residuum.
Dicarboxylic acid (A 2) comprise for example aliphatic dicarboxylic acid, for example oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane-α, alpha, omega-dicarboxylic acid, dodecane-α, alpha, omega-dicarboxylic acid, cis and trans cyclohexane-1,2-dicarboxylic acid, cis and trans cyclohexane-1,3-dicarboxylic acid, cis and trans cyclohexane-1,4-dicarboxylic acid, cis and trans pentamethylene-1,2-dicarboxylic acid, cis and trans pentamethylene-1, the 3-dicarboxylic acid.Can also use aromatic dicarboxylic acid, for example phthalic acid, m-phthalic acid and terephthalic acid in addition.Can also use unsaturated dicarboxylic acid, for example toxilic acid or fumaric acid.
Described dicarboxylic acid also can be by one or more following group replacement: C that are selected from 1-C 10Alkyl, C 3-C 12Cycloalkyl, alkylidene group be methylene radical or ethylidene for example, or C 6-C 14Aryl.The exemplary representative of the substituted dicarboxylic acid that can mention comprises following material: 2-Methylpropanedioic acid, 2-ethyl malonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethyl succsinic acid, 2-phenyl succsinic acid, methylene-succinic acid, 3,3-dimethylated pentanedioic acid.
Can also use the mixture of two or more above-mentioned dicarboxylic acid.
Described dicarboxylic acid can itself use also and can its derivative form use.
C 1-C 4Alkyl specifically means methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl, preferable methyl, ethyl and normal-butyl, more preferably methyl and ethyl, utmost point preferable methyl.
Can also use the mixture of dicarboxylic acid and one or more its derivatives.Can use the mixture of two or more different derivatives of one or more dicarboxylic acid equally.
Especially preferably use propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid or 1,4-cyclohexane dicarboxylic acid (hexahydrobenzene dioctyl phthalate), phthalic acid, m-phthalic acid, terephthalic acid or its mono alkyl ester or dialkyl.
Tricarboxylic acid that can react or polycarboxylic acid (D y) example comprise equisetic acid, 1,3,5-hexanaphthene tricarboxylic acid, 1,2,4-benzene tricarbonic acid, 1,3,5-benzene tricarbonic acid, 1,2,4,5-benzene tertacarbonic acid (1,2,4, the 5-pyromellitic acid) and mellitic acid and low-molecular-weight polypropylene acid.
Tricarboxylic acid or polycarboxylic acid (D y) can itself use also and can its derivative form use.
Derivative is corresponding acid anhydrides, mono alkyl ester or the dialkyl of monomer or polymer form, preferred single or two C 1-C 4Alkyl ester, more preferably list or dimethyl ester or corresponding list or diethyl ester, and single and divinyl ester also have mixed ester, preferably have different C 1-C 4The mixed ester of moieties, more preferably mixed methyl ethyl ester.
Can also use the mixture of tricarboxylic acid or polycarboxylic acid and one or more its derivatives, for example 1,2,4,5-pyromellitic acid and 1,2,4, the mixture of 5-pyromellitic acid dianhydride.Can use the mixture of two or more different derivatives of one or more tricarboxylic acid or polycarboxylic acid equally, for example 1,3,5-hexanaphthene tricarboxylic acid and 1,2,4, the mixture of 5-pyromellitic acid dianhydride.
Glycol (the B that uses 2) comprise for example ethylene glycol, the third-1, the 2-glycol, the third-1, the 3-glycol, fourth-1, the 2-glycol, fourth-1, the 3-glycol, fourth-1, the 4-glycol, fourth-2, the 3-glycol, penta-1, the 2-glycol, penta-1, the 3-glycol, penta-1, the 4-glycol, penta-1, the 5-glycol, penta-2, the 3-glycol, penta-2, the 4-glycol, oneself is-1 years old, the 2-glycol, oneself is-1 years old, the 3-glycol, oneself-1, the 4-glycol, oneself-1, the 5-glycol, oneself is-1 years old, the 6-glycol, oneself is-2 years old, the 5-glycol, heptan-1, the 2-glycol, 1, the 7-heptanediol, 1, the 8-ethohexadiol, 1, the 2-ethohexadiol, 1, the 9-nonanediol, 1, the 2-decanediol, 1, the 10-decanediol, 1, the 2-dodecanediol, 1, the 12-dodecanediol, 1,5-hexadiene-3, the 4-glycol, 1,2-encircles pentanediol and 1, and 3-encircles pentanediol, 1, the 2-cyclohexanediol, 1,3-cyclohexanediol and 1, the 4-cyclohexanediol, 1, two (methylol) hexanaphthenes of 1-, 1, two (methylol) hexanaphthenes of 2-, 1, two (methylol) hexanaphthenes and 1 of 3-, two (methylol) hexanaphthenes of 4-, 1, two (hydroxyethyl) hexanaphthenes of 1-, 1, two (hydroxyethyl) hexanaphthenes of 2-, 1, two (hydroxyethyl) hexanaphthenes and 1 of 3-, two (hydroxyethyl) hexanaphthenes of 4-, neopentyl glycol, (2)-and methyl-2, the 4-pentanediol, 2,4-dimethyl-2, the 4-pentanediol, 2-ethyl-1, the 3-hexylene glycol, 2,5-dimethyl-2,5-hexylene glycol, 2,2,4-trimethylammonium-pentanediol, tetramethyl ethylene ketone, glycol ether, triglycol, dipropylene glycol, tripropylene glycol, polyoxyethylene glycol HO (CH 2CH 2O) n-H or polypropylene glycol HO (CH[CH 3] CH 2O) n-H---n is integer and n 〉=4, poly-ethylidene-polypropylene glycol---sequence of oxyethane or propylene oxide be sectional or at random, polytetramethylene glycol---preferably have the molecular weight, poly--1 of the highest 5000g/mol, ammediol---preferably have molecular weight, the polycaprolactone of the highest 5000g/mol, or the mixture of two or more representatives of above-claimed cpd.One or two hydroxyl in the above-mentioned glycol can be substituted by the SH group.The preferred glycol that uses is an ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,2-cyclohexanediol, 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1, two (methylol) hexanaphthenes and 1 of 3-, two (methylol) hexanaphthenes of 4-, and glycol ether, triglycol, dipropylene glycol and tripropylene glycol, polyoxyethylene glycol HO (CH 2CH 2O) n-H or polypropylene glycol HO (CH[CH 3] CH 2O) nThe sequence of-H---n is integer and n 〉=4, poly-ethylidene-polypropylene glycol---oxyethane or propylene oxide is a sectional or at random, or polytetramethylene glycol---preferably have the molecular weight of the highest 5000g/mol.
Glycol B 2Can choose wantonly and also comprise other functionality for example carbonyl, carboxyl, alkoxy carbonyl or alkylsulfonyl, for example dimethylol propionic acid or dimethylolpropionic acid, with and C 1-C 4Alkyl ester, monostearin or glyceryl monooleate.
Alcohol (C with at least three functionality x) comprise glycerine, Pehanorm, trimethylolethane, TriMethylolPropane(TMP), 1,2, the 4-trihydroxybutane, three (methylol) amine, triethanolamine, tripropanolamine, tetramethylolmethane, Glycerol dimer, the higher degree condenses of triglycerin or glycerine, two (TriMethylolPropane(TMP)s), two (tetramethylolmethanes), isocyanuric acid trishydroxymethyl ester, isocyanuric acid trihydroxyethyl ester (THEIC), isocyanuric acid three hydroxypropyl esters, inositol or sugar, glucose for example, fructose or sucrose, sugar alcohol is Sorbitol Powder for example, mannitol, threitol, tetrahydroxybutane, adonitol (ribitol), arabitol (lysol sugar alcohol), Xylitol, galactitol (melampyrum), maltose alcohol, Palatinitol (isomalt), functionality is three or higher Aethoxy Sklerol, and it is three or higher alcohol or based on oxyethane based on functionality, propylene oxide and/or butylene oxide ring.
Special herein preferably glycerine, Glycerol dimer, triglycerin, trimethylolethane, TriMethylolPropane(TMP), two (TriMethylolPropane(TMP)), 1,2,4-trihydroxybutane, tetramethylolmethane, two (tetramethylolmethane), isocyanuric acid trihydroxyethyl ester, and based on the Aethoxy Sklerol of oxyethane and/or propylene oxide.
Reaction can be carried out under the situation that does not have or exist solvent.The example of suitable solvent comprises hydrocarbon for example paraffinic hydrocarbons, aromatics, ether and ketone.Preferred this is reflected under the situation that does not have solvent and carries out.Can carry out this reaction in the presence of water-removal agent, described water-removal agent adds when reaction begins as additive.Suitable example comprises molecular sieve, especially molecular sieve
Figure GPA00001139222000171
MgSO 4And Na 2SO 4Can also be by distilling and for example using the water sepn agent to remove water and/or alcohol in reaction process, water is removed by entrainment agent under the situation of using the water sepn agent.
This reaction can be carried out under the situation that does not have catalyzer.But preferably in the presence of at least a catalyzer, carry out.Described catalyzer is preferably tart organic catalyst, organo-metallic catalyst or organic catalyst, perhaps the mixture of two or more in tart organic catalyst, organo-metallic catalyst or the organic catalyst.
Be used for acid organic catalyst of the present invention and for example be sulfuric acid, vitriol and hydrosulfate for example sodium pyrosulfate, phosphoric acid, phosphonic acids, Hypophosporous Acid, 50, hydrazine aluminum sulfate, alum, acidic silica gel (pH≤6, especially≤5) and acidic alumina.Other spendable acid organic catalysts comprise that for example general formula is Al (OR 1) 3Aluminum compound, and titanate.Preferred acid organo-metallic catalyst for example is the ester of dialkyltin or dialkyl tin.Preferred acid organic catalyst is to contain for example acidic organic compound of bound phosphate groups, sulfonic acid group, sulfate group or phosphonyl group.Also can be with acid ion exchangers as acid organic catalyst.
This is reflected under 60 to 250 ℃ the temperature and carries out.
The hyper-branched polyester that the present invention uses has at least 500, preferred at least 600, the more preferably molecular weight M of 1000g/mol wMolecular weight M wThe upper limit be preferably 500000g/mol; Especially preferably be no more than 200000, extremely especially preferably be no more than 100000g/mol.
Polydispersity and number-average molecular weight and weight-average molecular weight M nAnd M wNumerical value use polymethylmethacrylate as standard substance and use tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE or hexafluoroisopropanol to measure by gel permeation chromatography here as eluent.This method is described in Analytiker Taschenbuch, vol.4, pages 433 to 442, Berlin1984.
The polydispersity of the polyester that the present invention uses is generally 1.2 to 50, and is preferred 1.4 to 40, and more preferably 1.5 to 30, extremely preferred 2 to 30.
The hyperbranched poly carbamate
The scope of term used herein " polyurethane(s) " has exceeded the implication of conventional understanding, comprises obtaining with the active hydrogen compounds reaction and can be by carboxylamine ester structure and the polymkeric substance that is connected of urea, allophanate, biuret, carbodiimide, acid amides, uretonimine (uretonimine), urea diketone (uretdione), isocyanuric acid ester or oxazolidone structure for example by vulcabond or polyisocyanates.
The hyperbranched poly carbamate that the present invention uses can use and contain isocyanate groups and can react the AB that is connected to form with isocyanate groups xMonomer is synthetic.Hyperbranched poly carbamate for synthetic the present invention uses can also use the monomer binding substances, and this monomer binding substances at first forms the AB as intermediate xStructural sections, wherein x is 2 to 8 natural number, preferred 2 or 3.The method that this hyperbranched poly carbamate and being used to prepares it is described in WO97/02304, by reference it is included in herein.Suitable hyperbranched poly carbamate also can and have at least two by vulcabond and/or polyisocyanates and can obtain with the reaction of the compound of the group of isocyanate reaction, wherein at least a reactant contains reactive different with the functional group of another reactant functional groups, and reaction conditions is chosen as and makes to have only some reactive group to react each other in each reactions steps.The method that such hyperbranched poly carbamate and being used to prepares it is described in EP 1026185, by reference it is included in herein.
Describedly can be preferably OH-, NH with the group of isocyanate reaction 2-, NHR-or SH group.
AB xMonomer can prepare by conventional methods.AB xMonomer can for example use the blocking group technology to synthesize by WO 97/02304 described method.This technology can be passed through by two isocyanic acids 2, and 4-toluylene ester (TDI) and TriMethylolPropane(TMP) prepare AB 2Monomeric process is carried out the example explanation.At first, TDI isocyanate groups for example is closed with the oxime reaction in a usual manner.Remaining free NCO group and TriMethylolPropane(TMP) react, but have only one and isocyanate groups reaction in three OH groups, and all the other two OH groups are closed by acetalization.Remove the molecule that blocking group obtains to have an isocyanate groups and two OH groups.
A particularly advantageous synthetic AB xThe mode of molecule is to use the method described in the DE-A 199 04 444, and group does not wherein need protection.Use vulcabond or polyisocyanates in this method, its with have at least two can with the compound reaction of the group of isocyanate reaction.At least a reactant contains reactive different with another reactant groups.Preferably, two kinds of reactants all contain reactive different with another reactant groups.Reaction conditions is chosen as and makes to have only some reactive group to react each other.
Available vulcabond and polyisocyanates comprise aliphatics well known in the prior art, annular aliphatic and aromatic isocyanate.Preferred vulcabond and polyisocyanates are 4, the mixture of the diphenylmethanediisocyanate of the diphenylmethanediisocyanate of 4 '-diphenylmethanediisocyanate, monomeric form and oligopolymer form (polymkeric substance MDI), tetramethylene diisocyanate, two isocyanic acids, six methylene esters, two isocyanic acids 4, the inferior diformazan phenyl ester of 4 '-methylene-bis (cyclohexyl) ester, two isocyanic acids, the inferior diformazan phenyl ester of two isocyanic acid tetramethyl-s, two isocyanic acid dodecane esters, two isocyanic acid Methionin alkyl esters---wherein alkyl is C 1-C 10Alkyl, two isocyanic acids 2,2,4-trimethylammonium-1,6-hexa-methylene ester or two isocyanic acids 2,4,4-trimethylammonium-1,6-hexa-methylene ester, 1,4-cyclohexyl diisocyanate or two isocyanic acid 4-isocyanatomethyls-1,8-eight methylene radical esters.
The vulcabond or the polyisocyanates that especially preferably have reactive different NCO groups, two isocyanic acids 2 for example, 4-methylene phenyl ester (2,4-TDI), two isocyanic acids 2,4 '-ditan ester (2,4 '-MDI), three TIs, two isocyanic acid isophorone esters (IPDI), two isocyanic acid 2-butyl-2-ethyl five methylene esters, isocyanic acid 2-propyl isocyanate base cyclohexyl, isocyanic acid 3 (4)-isocyanatomethyls-1-methyl cyclohexane ester, 1,4-two isocyanic acid 4-methylpentane esters, two isocyanic acids 2,4 '-methylene-bis (cyclohexyl) ester and 1,3-two isocyanic acid 4-methylcyclohexane esters (H-TDI).Also preferred especially such isocyanic ester (b), its NCO group have identical reactivity when initial but addition alcohol or amine can cause reactive reduction of the 2nd NCO group for the first time to the NCO group.The example passes through the delocalised electron system coupling for the NCO group, described delocalised electron system is two isocyanic acids 1 for example, inferior phenyl ester of 3-and two isocyanic acids 1, the inferior phenyl ester of 4-, two isocyanic acids 1, the inferior naphthalene ester of 5-, two isocyanic acid diphenyl esters, two isocyanic acid tolidine esters or two isocyanic acids 2,6-toluene ester.
Can also use for example can be by the low polymeric polyisocyanate or the polymeric polyisocyanate of described vulcabond or polyisocyanates or the preparation of its mixture, and described low polymeric polyisocyanate or polymeric polyisocyanate are connected by carbamate, allophanate, urea, biuret, urea diketone, acid amides, isocyanuric acid ester, carbodiimide, uretonimine, oxadiazine triketone or iminooxadiazinedionepolyisocyanates diketone structure.
Used have at least two two reactive different senses, trifunctional or four functional compounds that can be preferably its functional group and NCO group with the compound of the group of isocyanate reaction.The compound that preferably has at least one primary hydroxyl and at least one secondary hydroxyl, at least one hydroxyl and at least one sulfydryl, have at least one hydroxyl and at least one amino compound in the preferred especially molecule, especially amino alcohol, aminodiol and amino triol are because amino than the obvious easier and isocyanate reaction of hydroxyl.
It is described that to have at least two can be propylene glycol, glycerol, mercaptoethanol, thanomin, N-Mono Methyl Ethanol Amine, diethanolamine, ethanol propanol amine, dipropanolamine, diisopropanolamine (DIPA), 2-amino-1 with the examples for compounds of the group of isocyanate reaction, ammediol, 2-amino-2-methyl-1, ammediol or three (methylol) aminomethane.Also can use the mixture of described compound.
AB 2The preparation of molecule can be carried out the example explanation by the reaction of vulcabond and aminodiol.At first one mole of vulcabond and one mole of aminodiol react at low temperatures, preferably in-10 to 30 ℃ scope.Form being reflected in this temperature range of carbamate and be suppressed substantially fully, the reactive higher NCO group in the isocyanic ester only with aminodiol in amino react.The AB that forms xMolecule has a free NCO group and two free OH groups, can be used for synthetic highly branched polyurethane(s).
When heating and/or adding catalyzer, this AB 2Molecule can carry out intermolecular reaction, forms highly branched polyurethane(s).The synthetic of hyperbranched poly carbamate can advantageously do not isolated AB in advance xUnder the situation of molecule, further carrying out at elevated temperatures in the reactions steps, the temperature of described rising is preferably in 30 to 80 ℃ scope.Use above-mentioned AB with two OH groups and a NCO group 2Molecule can generate the hyperbranched polymer that per molecule has the OH group of a free NCO group and---depending on the polymerization degree---some amount.This reaction can be carried out paramount degree of conversion to generate the structure of ultra high molecular weight.But also can be for example by adding suitable monofunctional compound or being used to prepare AB by interpolation 2One of initial compounds of molecule is stopped reaction when having reached the desired molecule amount.According to the initial compounds that is used for termination reaction, can obtain end capped molecule of complete NCO or the complete end capped molecule of OH.
Perhaps, also can be for example by one mole of glycerol and 2 mole 2,4-TDI prepares AB 2Molecule.The preferential reaction at low temperatures of primary alcohol group and 4 s' isocyanate groups forms the adducts with an OH group and two isocyanate groups, and this adducts at high temperature is converted into the hyperbranched poly carbamate as described.Its initial hyperbranched polymer that generates NCO group with a free OH group and---depending on polymkeric substance---some amount.
The hyperbranched poly carbamate can prepare under solvent-free situation usually, but preferably prepares in solution.It is the inert compound for liquid state and to described monomer and polymkeric substance at room temperature that the available solvent generally includes all.
Can obtain other products by further synthetic schemes.Can be for example by vulcabond with have at least 4 and can obtain AB with the reaction of the group of isocyanate reaction 3Molecule.An example is two isocyanic acids 2, the reaction of 4-toluene ester and three (methylol) aminomethane.
Polyreaction also can be used and can stop with the polyfunctional compound of each A radical reaction.Thereby a plurality of little super branched molecules can be coupled together to form big super branched molecule.
Hyperbranched poly carbamate with side chain that chain is extended can for example be used for polyreaction and AB by use xThe mol ratio of molecule is 1: 1 vulcabond and has two and can obtain with the compound of the group of isocyanate reaction.These AA or BB compound also can have other functional group, but these functional groups must can not be under selected reaction conditions and A or B radical reaction.This makes it possible to introduce other functionality in hyperbranched polymer.
Other synthetic schemess that are used for the hyperbranched poly carbamate are disclosed in DE 100 13 187 and DE 100 30 869.
As mentioned above, the functional group of the hyperbranched poly carbamate that obtains by building-up reactions also can be by hydrophobization, hydrophilization or sense exchange (transfunctionalization).According to its reactivity, the hyperbranched poly carbamate that contains isocyanate groups is particularly useful for the sense exchange.Can also be by suitable reaction compatibility material to OH end-blocking or NH 2End capped polyurethane(s) carries out the sense exchange.
The preferred group of introducing the hyperbranched poly carbamate is-COOH ,-CONH 2,-OH ,-NH 2,-NHR ,-NR 2,-NR 3 +,-SO 3H and salt thereof.
Group with enough tart H atoms can be by being converted into corresponding salt with suitable alkali.Similarly, base groups can use suitable acid to be converted into corresponding salt.Therefore can obtain water-soluble hyperbranched poly carbamate.
By making end capped product of NCO and alkohol and amine, especially having a C 8-C 40The alkohol and amine reaction of alkyl can obtain the hydrophobization product.
Hydrophobic but non-ionic product can obtain by end capped polymkeric substance of NCO and Aethoxy Sklerol reaction, and described Aethoxy Sklerol is glycol ether, triglycol, Tetraglycol 99 or polyoxyethylene glycol for example.
Acidic group can be for example by being included into hydroxycarboxylic acid, hydroxyl sulfoacid or amino acid reaction.The example of suitable reaction compatibility thing is 2-oxyacetic acid, 4-hydroxy-benzoic acid, sabinic acid, 2-ethylenehydrinsulfonic acid, glycine or L-Ala.
Can also generate hyperbranched poly carbamate with different functionality.This can be by for example realizing with the mixture reaction of multiple compound or by for example only a part of OH of functional group and/or the NCO radical reaction that only make the initial existence of a part.
The sense exchange of hyperbranched poly carbamate can advantageously be carried out immediately after polyreaction and in advance the end capped polyurethane(s) of NCO do not separated.But functionalizedly also can in other reaction, carry out.
The hyperbranched poly carbamate that uses among the present invention on average has at least 4 and be no more than 100 functional groups usually.Described hyperbranched poly carbamate preferably has 8 to 80, more preferably 8 to 50 functional groups.The weight-average molecular weight M of the preferred hyperbranched poly carbamate that uses wBe 1000 to 500000g/mol, preferred 5000 to 200000g/mol, and more preferably 10000 to 100000g/mol.
Hyperbranched polyureas
The hyperbranched polyureas of high functionality that can be used as the component that increases glossiness in the present invention can obtain by the amine reaction that for example makes one or more carbonic ethers and one or more have two primary aminos and/or secondary amino group at least, and wherein at least a amine has at least three primary aminos and/or secondary amino group.
Suitable carbonic ether is aliphatics, aromatic series or mixing-in fat family-aromatic carbonate; The preferred aliphat carbonic ether for example has C 1-C 12The dialkyl carbonate of alkyl.Example is an ethylene carbonate, 1,2-Texacar PC or 1, the two dodecyl esters of 3-Texacar PC, diphenyl carbonate, carboxylol ester, carbonic acid dinaphthyl ester, carbonic acid ethyl phenyl ester, dimethyl benzyl, methylcarbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, carbonic acid diisobutyl ester, diamyl carbonate, carbonic acid dihexyl, carbonic acid two heptyl esters, carbonic acid dioctyl ester, carbonic acid didecyl ester or carbonic acid.Especially preferably the carbonic ether that uses is methylcarbonate, diethyl carbonate, dibutyl carbonate and carbonic acid diisobutyl ester.
Carbonic ether and one or more have the amine reaction of at least two primary aminos and/or secondary amino group, and wherein at least a amine has at least three primary aminos and/or secondary amino group.Amine with two primary aminos and/or secondary amino group produces chainpropagation in polyureas, and the amine with three or more primary amino or secondary amino group causes the branching of the hyperbranched polyureas of gained high functionality.
Suitable can for example be quadrol with the amine with two primary aminos or secondary amino group of carbonate group or carbamate groups reaction, N-alkyl quadrol, propylene diamine, 2,2-dimethyl-1, the 3-propylene diamine, N-alkyl propylene diamine, butanediamine, N-alkyl butanediamine, pentamethylene diamine, hexanediamine, N-alkyl hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, the dodecane diamines, the n-Hexadecane diamines, tolylene diamine, dimethylphenylene diamine, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, cyclohexanediamine, two (amino methyl) hexanaphthene, diamino diphenyl sulfone, isophorone diamine, 2-butyl-2-ethyl-1, the 5-five methylene diamine, 2,2,4-trimethylammonium-1,6-hexanediamine or 2,4,4-trimethylammonium-1, the 6-hexanediamine, 2-aminopropyl cyclo-hexylamine, 3 (4)-aminomethyl-1,2s-methylcyclohexyl amine, 1,4-diamino-4-methylpentane, end capped polyoxy sub alkyl polylol of amine (being called Jeffamine) or the end capped polytetramethylene glycol of amine.
Described amine preferably has two primary aminos, quadrol for example, propylene diamine, 2,2-dimethyl-1, the 3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, the dodecane diamines, the n-Hexadecane diamines, tolylene diamine, dimethylphenylene diamine, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, cyclohexanediamine, diamino diphenyl sulfone, isophorone diamine, 2,2,4-trimethylammonium-1,6-hexanediamine or 2,4,4-trimethylammonium-1, the 6-hexanediamine, 2-aminopropyl cyclo-hexylamine, 2-aminopropyl cyclo-hexylamine, 3 (4)-aminomethyl-1,2s-methylcyclohexyl amine, 1,4-diamino-4-methylpentane, end capped polyoxy sub alkyl polylol of amine (being called Jeffamine) or the end capped polytetramethylene glycol of amine.
Preferred especially butanediamine, pentamethylene diamine, hexanediamine, tolylene diamine, dimethylphenylene diamine, diaminodiphenyl-methane, diamino-dicyclohexyl methane, phenylenediamine, cyclohexanediamine, diamino diphenyl sulfone, isophorone diamine, two (amino methyl) hexanaphthene, the end capped polyoxy sub alkyl polylol of amine (being called Jeffamine) or the end capped polytetramethylene glycol of amine.
Suitable can for example be three (amino-ethyl) amine with the amine with three or more primary amino and/or secondary amino group of carbonate group or carbamate groups reaction, three (aminopropyl) amine, three (amino hexyl) amine, the triamino hexane, the 4-aminomethyl-1,2,8-eight methylene diamine, triaminononane, two (amino-ethyl) amine, two (aminopropyl) amine, two (amino butyl) amine, two (amino amyl group) amine, two (amino hexyl) amine, N-(2-amino-ethyl) propylene diamine, trimeric cyanamide, oligomeric diaminodiphenyl-methane, N, N '-two (3-aminopropyl) quadrol, N, N '-two (3-aminopropyl) butanediamine, N, N, N ', N '-four (3-aminopropyl) quadrol, N, N, N ', N '-four (3-aminopropyl) butanediamine, functionality is three or the higher end capped polyoxy sub alkyl polylol of amine (being called Jeffamine), functionality be three or higher polymine or functionality be three or higher polypropylen(e)imine.
The amine that preferably has three or more primary amino and/or secondary amino group is three (amino-ethyl) amine, three (aminopropyl) amine, three (amino hexyl) amine, triamino hexane, 4-aminomethyl-1,2, and 8-eight methylene diamine, triaminononane, two (amino-ethyl) amine, two (aminopropyl) amine, two (amino butyl) amine, two (amino amyl group) amine, two (amino hexyl) amine, N-(2-amino-ethyl) propylene diamine, trimeric cyanamide or functionality are three or the higher end capped polyoxy sub alkyl polylol of amine (being called Jeffamine).
The amine that especially preferably has three or more primary aminos, for example three (amino-ethyl) amine, three (aminopropyl) amine, three (amino hexyl) amine, triamino hexane, 4-aminomethyl-1,2,8-eight methylene diamine, triaminononane or functionality are three or the higher end capped polyoxy sub alkyl polylol of amine (being called Jeffamine).
What will know is that the mixture of described amine also can use.
Usually not only use amine, also use amine with three or more primary amino or secondary amino group with two primary aminos or secondary amino group.This amine mixt also can characterize by its average amine functionality, and non-reacted uncle's amino is not counted in.Therefore, for example diamines and triamine etc. the average functionality of molar mixture be 2.5.Preferred average amine functionality is the present invention's reaction of 2.1 to 10, particularly 2.1 to 5 amine mixt.
Carbonic ether is finished by alcohol or phenol that the cancellation carbonic ether is connected with the reaction that diamines or polyamine form the hyperbranched polyureas of high functionality of the present invention's use.If the amino reaction of a part carbonic ether and two, then cancellation two molecule alcohol or phenol and generate a urea groups.If a part carbonic ether only reacts with an amino, then generate carbamate groups and cancellation a part alcohol or phenol.
The reaction of a kind of carbonic ether or multiple carbonic ether and a kind of amine or various kinds of amine can be carried out in solvent.In this case, can use usually and any each reactant is the inert solvent.Preferably carry out in organic solvent, described organic solvent is decane, dodecane, benzene, toluene, chlorobenzene, dichlorobenzene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or solvent naphtha for example.
In a preferred embodiment, be reflected in the body and carry out, promptly do not have inert solvent.If alcohol that discharges in reaction between amine and carbonic ether or the carbamate or phenol can be isolated, thereby remove from molecular balance by distillation---being suitably under the pressure of reduction---.This also can add fast response.
In order to accelerate the reaction between amine and carbonic ether or the carbamate, also can add catalyzer or catalyst mixture.Appropriate catalyst is generally the compound of the formation of catalytic amino manthanoate or urea, for example alkali metal hydroxide or alkaline earth metal hydroxides, alkali metal hydrocarbonate or alkali metal bicarbonates, alkaline carbonate or alkaline earth metal carbonate, tertiary amine, ammonium compound, or the organic compound of aluminium, tin, zinc, titanium, zirconium or bismuth.For example can use the oxyhydroxide of lithium, sodium, potassium or caesium, Quilonum Retard, yellow soda ash, salt of wormwood or cesium carbonate, diazabicyclo octane (DABCO), diazabicyclo-nonene (DBN), diazabicyclo undecylene (DBU), imidazoles be imidazoles, 1-Methylimidazole, glyoxal ethyline and 1,2 dimethylimidazole for example, four butanols titaniums, Dibutyltin oxide, dibutyl tin dilaurate, two stannous octoates, methyl ethyl diketone zirconium, or the mixture of these materials.
Catalyzer adds with the amount of 50 to 10000 ppm by weight, preferred 100 to 5000 ppm by weight usually, and described amount is based on the amount meter of used amine.
After the reaction, promptly do not carry out further modification, with the hyperbranched polyureas of the high functionality amino or the carbamate groups end-blocking of present method preparation.It can easily be dissolved in polar solvent, water for example, and alcohol is methyl alcohol, ethanol, butanols for example, alcohol/water mixture, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, ethylene carbonate or Texacar PC.
Be used for the hyperbranched polyureas of high functionality of the present invention and be containing urea groups and at least four, preferred at least six, the particularly product of at least eight functional groups.Usually the number of functional group does not have the upper limit, but the product of the functional group more than having very may demonstrate undesired character, for example high viscosity or low solubility.The high functionality polyureas that the present invention uses has usually and is no more than 100 functional groups, preferably is no more than 30 functional groups.The implication of functional group is primary amino, secondary amino group or uncle's amino or carbamate groups herein.In addition, the hyperbranched polyureas of high functionality can contain other functional groups, and described other functional groups do not participate in synthetic (the seeing below) of hyperbranched polymer.These other functional groups can introduce by the diamines or the polyamine that also contain other functional groups except primary amino and secondary amino group.
The polyureas that the present invention uses can contain other functional groups.Functionalized can carrying out in the process of carbonic ether and a kind of amine or various kinds of amine reaction in this case promptly carries out in the polycondensation process that molecular weight increases, and be perhaps after polycondensation finishes, follow-up functionalized by the gained polyureas is carried out.
If before molecular weight increases or during add the component that except amino or carbamate groups, also contains other functional groups, then product is to contain other of stochastic distribution---promptly except carbamate groups or amino---polyureas of functional group.
For example, before the polycondensation or during, can add the component that except amino or carbamate groups, also contains hydroxyl, sulfydryl, uncle's amino, ether, carboxyl, sulfonic group, phosphonate group, aryl or chain alkyl.
The component that is used for functionalized hydroxyl be can be added and for example product, 4-hydroxy piperidine, 1-hydroxyethyl piperazine, diethanolamine, dipropanolamine, diisopropanolamine (DIPA), three (methylol) aminomethane or three (hydroxyethyl) aminomethane of the more high alkoxy degree of thanomin, N-Mono Methyl Ethanol Amine, Propanolamine, Yi Bingchunan, butanolamine, 2-amino-1-butanols, 2-(fourth amino) ethanol, 2-(hexamethylene amino) ethanol, 2-(2 '-amino ethoxy) ethanol or ammonia comprised.
Can be added and be used for the functionalized component that contains sulfydryl and comprise for example cysteamine.By uncle's amino, can be by using for example N-methyl diethylenetriamine or N, N-dimethyl ethylene diamine is functionalized with hyperbranched polyureas.By ether group, can be by using amine terminated polyether alcohol (being called Jeffamine) that hyperbranched polyureas is functionalized.By acidic group, can for example aminocarboxylic acid, thionamic acid or aminophosphonic acid be functionalized with hyperbranched polyureas by using.By chain alkyl, it is functionalized with hyperbranched polyureas to have the alkylamine or an alkyl isocyanate of chain alkyl by use.
Polyureas also can be undertaken functionalized by using a spot of monomer that contains the functional group that is different from amino or carbamate groups.Can mention for example having two, three or the alcohol of high functionality more this moment, described alcohol can be included into polyureas by carbonic ether or carbamate-functional.Therefore, for example can obtain hydrophobicity, and polyethylene oxide glycol or triol make the polyureas possess hydrophilic property by adding long-chain alkane glycol, enediol or alkyne diol.
Described before the polycondensation or during the functional group except that amine, carbonic ether or carbamate groups that introduces usually with 0.1 to 80mol%, preferred 1 to 50mol% amount introduces, described amount is based on the total amount meter of amino, carbamate and carbonate group.
Containing the follow-up functionalized of the amino hyperbranched polyureas of high functionality can contain the molecule of acidic group, isocyanate groups, ketone group or aldehyde radical or contain for example molecule realization of acrylic double bond of activity double key by for example adding.For example, if can obtain to contain the polyureas of acidic group by reaction and suitable then being hydrolyzed with vinylformic acid or toxilic acid and derivative thereof.
In addition, can will contain the amino hyperbranched polyureas of high functionality by for example oxyethane, propylene oxide or butylene oxide ring reaction are converted into the high functionality polyurea polylol with oxirane.
Form salt with protonic acid or for example methyl halide or sulfuric acid dialkyl carry out quaternizedly the hyperbranched polyureas of high functionality being dissolved in maybe can be scattered in water to amido functional group with alkylating reagent.
In order to carry out hydrophobization, can make hyperbranched polyureas of the end capped high functionality of amine and saturated or unsaturated long-chain carboxylic acid, its can with derivative or the aliphatics or the aromatic isocyanate reaction of amine groups reaction.
The end capped polyureas of carbamate groups can be by reacting and hydrophobization with chain alkyl amine or long-chain fat family monohydroxy-alcohol.
Ultrabranching polyamide
Suitable ultrabranching polyamide can be by making first monomer A with at least two functional group A 2With second monomers B with at least three B of functional group 3Prepared in reaction, wherein
1) functional group A and B react each other, and
2) one of monomer A and B are that amine and another are carboxylic acid or acrylate.
Suitable ultrabranching polyamide comprises ultrabranching polyamide base amine (referring to EP-A 802215, US 2003/0069370A1 and US 2002/0161113A1).
Though first monomer A 2Also can have more than two functional group A, but herein for writing A for purpose of brevity 2Although, and second monomers B 3Also can have more than three B of functional group, but herein for writing B for purpose of brevity 3Important factor only is A 2And B 3The functionality difference.
According to condition 1), functional group A and B react each other.Therefore the selection of functional group A and B should make A not react (perhaps only with inapparent degree reaction) with B with A reaction (perhaps only with inapparent degree reaction) and B, but A and B reaction.
According to condition 2), one of monomer A and B are that amine and another are carboxylic acid.
Preferably, monomer A 2For having the carboxylic acid of at least two carboxyls, and monomers B 3For having the amine of at least three amino.Perhaps monomer A 2For having the amine of at least two amino, and monomers B 3For having the carboxylic acid of at least three carboxyls.
Suitable carboxylic acid has 2 to 4 usually, 2 or 3 carboxyls particularly, and has alkyl, aryl or the arylalkyl that contains 1 to 30 C atom.
The example of spendable dicarboxylic acid is: oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane-α, alpha, omega-dicarboxylic acid, dodecane-α, alpha, omega-dicarboxylic acid, cis and trans cyclohexane-1,2-dicarboxylic acid, cis and trans cyclohexane-1,3-dicarboxylic acid, cis and trans cyclohexane-1,4-dicarboxylic acid, cis and trans pentamethylene-1,2-dicarboxylic acid and cis and trans pentamethylene-1,3-dicarboxylic acid, described dicarboxylic acid also can be by one or more following group replacement: C that are selected from 1-C 10Alkyl, C 3-C 12Cycloalkyl, alkylidene group and C 6-C 14Aryl.The example of the substituted dicarboxylic acid that can mention is: 2-Methylpropanedioic acid, 2-ethyl malonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethyl succsinic acid, 2-phenyl succsinic acid, methylene-succinic acid and 3,3-dimethylated pentanedioic acid.
Other suitable compound are carboxylic acid for ethylenic is unsaturated, for example toxilic acid and fumaric acid, and aromatic dicarboxylic acid, for example phthalic acid, m-phthalic acid or terephthalic acid.
The suitable tricarboxylic acid or the example of tetracarboxylic acid are 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4,5-pyromellitic acid, butane tricarboxylic acid, naphthalene tricarboxylic acid and hexanaphthene-1,3,5-tricarboxylic acid.
Can also use the mixture of two or more above-mentioned carboxylic acids.Described carboxylic acid can itself use also and can its derivative form use.Described derivative particularly
The acid anhydrides of-described carboxylic acid, especially monomeric form or polymer form;
The ester of-described carboxylic acid, for example
Mono alkyl ester or dialkyl, preferred mono-methyl or dimethyl ester, perhaps corresponding mono ethyl ester or diethyl ester, perhaps mono alkyl ester or the dialkyl that generates by higher alcohols more, described more higher alcohols is n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, n-hexyl alcohol for example
Single vinyl acetate and divinyl ester, and
Mixed ester, the preferable methyl ethyl ester.
Can also use the mixture of forming by the mixture of two or more different derivatives of its derivative of carboxylic acid and one or more or one or more dicarboxylic acid.
Used carboxylic acid more has choosing to comprise succsinic acid, pentanedioic acid, hexanodioic acid, cyclohexane dicarboxylic acid, phthalic acid, m-phthalic acid, terephthalic acid or its mono-methyl or dimethyl ester.Preferred extremely especially succsinic acid and hexanodioic acid.
Suitable amine has 2 to 6 usually, 2 to 4 amino particularly, and alkyl, aryl or arylalkyl with 1 to 30 C atom.
The example of available diamines is formula R 1-NH-R 2-NH-R 3Diamines, R wherein 1, R 2And R 3Be hydrogen or alkyl, aryl or arylalkyl independently of one another with 1 to 20 C atom.Described alkyl can be linear or R particularly 2Also can be cyclic.
The example of suitable diamines is a quadrol, propylene diamine (1,2-diaminopropanes and 1, the 3-diaminopropanes), N-methyl ethylene diamine, piperazine, tetramethylene-diamine (1, the 4-diaminobutane), N, N '-dimethyl ethylene diamine, N-ethyl ethylene diamine, 1,5-diamino pentane, 1,3-diamino-2, the 2-diethyl propane, 1, two (methylamino-) propane of 3-, hexamethylene-diamine (1, the 6-diamino hexane), 1,5-diamino-2, the 2-dimethylpentane, 3-(third amino) propylamine, N, N '-two (3-aminopropyl) piperazine, N, N '-two (3-aminopropyl) piperazine, and isophorone diamine (IPDA).
Suitable triamine, tetramine or more the amine of high functionality be three (2-amino-ethyl) amine, three (2-aminopropyl) amine, diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), isopropylidene triamine, dipropylenetriamine and N, N '-two (3-aminopropyl ethylene diamine).
Aminobenzyl amine and amino hydrazides with 2 or a plurality of amino also are suitable.
Used amine preferably includes DETA or three (2-aminopropyl) amine or its mixture especially.
Can also use the mixture of two or more carboxylic acids or carboxylic acid derivative or the mixture of two or more amine.The functionality of described various carboxylic acid or amine can be identical or different.
Particularly, if monomer A 2Be diamines, then used monomers B 3The mixture that can comprise dicarboxylic acid and tricarboxylic acid (or more the carboxylic acid of high functionality), mixture B 3Average functionality be at least 2.1.For example, the average functionality of the mixture of being made up of 50mol% dicarboxylic acid and 50mol% tricarboxylic acid is 2.5.
Similarly, if monomer A 2Be dicarboxylic acid, then used monomers B 3The mixture that can comprise diamines and triamine (or more the amine of high functionality), mixture B 3Average functionality be at least 2.1.This scheme is particularly preferred.For example, the average functionality of the mixture of being made up of 50mol% diamines and 50mol% triamine is 2.5.
Monomer A 2The reactivity of functional group A can be identical also can be different.Equally, monomers B 3The reactivity of the B of functional group can be identical also can be different.Particularly, monomer A 2The reactivity or the monomers B of two amino 3The reactivity of three amino can be identical or different.
In a preferred embodiment, carboxylic acid is two functional monomer A 2, amine is trifunctional monomer B 3, this means preferred use dicarboxylic acid and triamine or the amine of high functionality more.
Used monomer A 2More preferably comprise dicarboxylic acid, used monomers B 3More preferably comprise triamine.Used monomer A 2The utmost point preferably includes hexanodioic acid and used monomers B 3The utmost point preferably includes diethylenetriamine or three (2-aminopropyl) amine.
In monomer A 2And B 3Polymerization is with in the process that generates ultrabranching polyamide or afterwards, also can use two senses or more the monomer C of high functionality as chain extension agent.This make can controlling polymers jellying point (form the transition point of insoluble gel particle by crosslinking reaction; For example referring to Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, pp.387-398), and change macromolecular structure, i.e. the connection of monomer side chain.
Therefore, present method embodiment preferred is also in monomer A 2And B 3Between the reaction period or use monomer C afterwards as chain extension agent.
The suitable example that increases chain monomer C is the above-mentioned diamines or the amine of high functionality more, thereby its carboxyl reaction with different polymkeric substance side chains connects.Specially suitable compound is an isophorone diamine, quadrol, 1, the 2-diaminopropanes, 1, the 3-diaminopropanes, N-methyl ethylene diamine, piperazine, tetramethylene-diamine (1, the 4-diaminobutane), N, N '-dimethyl ethylene diamine, N-ethyl ethylene diamine, 1,5-diamino pentane, 1,3-diamino-2, the 2-diethyl propane, 1, two (methylamino-) propane of 3-, hexamethylene-diamine (1), 1,5-diamino-2-methylpentane, 3-(third amino) propylamine, N, N '-two (3-aminopropyl) piperazine, N, N '-two (3-aminopropyl) piperazine and isophorone diamine (IPDA).
General formula H 2The amino acid of N-R-COOH also is suitable as chain extension agent C, and wherein R is an organic group.
The amount of chain extension agent C depends on required jellying point or required macromolecular structure usually.The amount of chain extension agent C is generally 0.1 weight % to 50 weight %, and preferred 0.5 weight % to 40 weight %, particularly 1 weight % to 30 weight % are based on used monomer A 2And B 3The total amount meter.
In order to prepare the functionalized poly acid amides, also use simple function comonomer D, it can be in monomer A 2And B 3Reaction before, during or add afterwards.This method obtains by the polymkeric substance of copolymerization units and functional group's chemistry modification thereof.
Therefore a preferred embodiment of present method is in monomer A 2And B 3Reaction before, during or use comonomer D afterwards with functional group, and generate modified polyamide.
The example of described comonomer D is saturated or unsaturated monocarboxylic, comprises lipid acid and acid anhydrides thereof or ester.The example of suitable acid is acetate, propionic acid, butyric acid, valeric acid, isopropylformic acid, trimethylacetic acid, caproic acid, sad, enanthic acid, capric acid, n-nonanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, montanic acid, stearic acid, Unimac 5680, n-nonanoic acid, 2 ethyl hexanoic acid, phenylformic acid, and unsaturated monocarboxylic, methacrylic acid for example, and the acid anhydrides of described monocarboxylic acid and ester, for example acrylate or methacrylic ester.
The example of suitable unsaturated fatty acids D is oleic acid, ricinolic acid, linolic acid, linolenic acid, erucic acid, and the lipid acid that derives from soybean, linseed oil, Viscotrol C and Sunflower Receptacle.
Specially suitable carboxylicesters D is methyl methacrylate, hydroxyethyl methylacrylate and Rocryl 410.
Spendable other comonomers D is an alcohol, comprise Fatty Alcohol(C12-C14 and C12-C18), for example glyceryl monolaurate, monostearin, ethylene glycol monomethyl ether, poly-ethylidene monomethyl ether, phenylcarbinol, 1-dodecanol, 1-tetradecanol, 1-cetyl alcohol, and unsaturated fatty alcohol.
Other suitable comonomer D are acrylate, alkyl acrylate particularly, for example butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid Lauryl Ester, stearyl acrylate base ester, or acrylic acid hydroxy alkyl ester, for example Hydroxyethyl acrylate, Propylene glycol monoacrylate and vinylformic acid hydroxy butyl ester.Acrylate can a kind of simple especially mode be introduced into polymkeric substance by Michael addition at the amino place of ultrabranching polyamide.
The amount of comonomer D depends on that usually polymkeric substance treats the degree of modification.The amount of comonomer D is generally 0.5 weight % to 40 weight %, and preferred 1 weight % to 35 weight % is based on used monomer A 2And B 3The total amount meter.
According to used monomeric property quality and quantity, and according to reaction conditions, ultrabranching polyamide can have terminal carboxyl(group) (COOH) or terminal amino group (NH, NH 2) or the two all have.Be added the selection that is used for functionalized comonomer D and depend on the character and the number of the end group that reacts with D usually.If C-terminal is group modified, then to every mole of C-terminal group preferably use 0.5 to 2.5, the amine of preferred 0.6 to 2, preferred especially 0.7 to 1.5 molar equivalent for example monoamine or diamines, particularly have a triamine of primary amino or secondary amino group.
If N-terminal is group modified, to every mole of amino end group preferably use 0.5 to 2.5, the monocarboxylic acid of preferred 0.6 to 2, preferred especially 0.7 to 1.5 molar equivalent.
As mentioned above, also Michael addition can be used so that N-terminal group and described acrylate reactions, the numerical value of the acrylate molar equivalent of Shi Yonging is for to be preferably 0.5 to 2.5 with respect to every mole of amino end group for this purpose, and particularly 0.6 to 2, more preferably 0.7 to 1.5.
Free COOH group number (acid number) in the final polyamide products is generally 0 to 400, preferred 0 to 200mgKOH/ and restrains polymkeric substance, and it can for example record by titration according to DIN 53240-2.
Monomer A 2Usually and monomers B 3Reaction at elevated temperatures, for example 80 to 180 ℃, particularly 90 to 160 ℃.Preferably rare gas element for example in nitrogen or the vacuum, exist or do not exist under the situation of solvent and operating, described solvent is water, 1 for example, 4-diox, dimethyl formamide (DMF) or N,N-DIMETHYLACETAMIDE (DMAC).Example with solvent mixture of good solubility is by water and 1, the solvent mixture that the 4-diox is formed.Yet, must not use solvent; For example, can be with carboxylic acid as initial charge and with its fusion, and amine can be added in the melt.The water that is generated by reaction in polymerization (polycondensation) process for example can be extracted out in a vacuum, or use suitable solvent for example toluene remove by component distillation.
Pressure is inessential usually, for example is 1mbar to 100bar absolute pressure.If do not use solvent, then the reaction in water simply mode by in a vacuum for example 1 to 500mbar time operation remove.
Reaction times is generally 5 minutes to 48 hours, and preferred 30 minutes to 24 hours, more preferably 1 hour to 10 hours.
The reaction of carboxylic acid and amine can be carried out under the situation that does not have or exist catalyzer.The example of appropriate catalyst is an amidation catalyst hereinafter described.
If also use catalyzer, then its amount is generally 1 to 5000 ppm by weight, and preferred 10 to 1000 ppm by weight are based on monomer A 2And B 3The total amount meter.
During polymerization process or afterwards, can add described chain extension agent C if desired.In order to carry out the chemical modification of ultrabranching polyamide, can also before the polymerization process, during or add described comonomer D afterwards.
The available if desired conventional amidation catalyst catalysis of the reaction of comonomer D.The example of described catalyzer is ammonium phosphate, triphenyl phosphite or dicyclohexylcarbodiimide.Particularly, when using heat sensitivity comonomer D, and when using methacrylic ester or Fatty Alcohol(C12-C14 and C12-C18) as comonomer D, reaction also can be by enzyme catalysis, common 40 to 90 ℃, preferred 50 to 85 ℃, particularly in the presence of free radical inhibitors, operate under 55 to 80 ℃.
If undesirable crosslinking reaction of radical polymerization and unsaturated functional group is by inhibitor and suitablely be suppressed by operating in rare gas element.The example of described inhibitor is a quinhydrones, the monomethyl ether of quinhydrones, thiodiphenylamine, amphyl is the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2 for example, 4-xylenol, perhaps N--oxyl (oxyl) compound N--oxyl-4-hydroxyl-2 for example, 2,6,6-tetramethyl piperidine (hydroxyl-TEMPO), N--oxyl-4-oxygen-2,2,6,6-tetramethyl piperidine (TEMPO), its amount are 50 to 2000 ppm by weight, based on monomer A 2And B 3The total amount meter.
Preparation process is preferably with intermittent mode or can be in a continuous manner, in stirred vessel for example, carry out in the tubular reactor, in the tower reactor or in other popular response devices, described reactor can have static state or dynamic mixer and be used for pressure-controlling and temperature control and the conventional equipment operated at rare gas element.
When operating under solvent-free situation, end product directly obtains usually, and if necessary, can carry out purifying by conventional purification process.If used solvent, then can after reaction, from reaction mixture, remove by conventional methods and desolvate, for example by vacuum distilling.
The characteristics of the inventive method are easy especially.It makes it possible to prepare ultrabranching polyamide with simple one pot reaction.Need not the blocking group of intermediate or intermediate is carried out isolated or purified.Present method is favourable economically, because monomer can be buied and be cheap.
The hyperbranched poly esteramides
Suitable hyperbranched poly esteramides can be by making the carboxylic acid with at least two carboxyls and the amino alcohol prepared in reaction with at least one amino and at least two hydroxyls.
This method originates in carboxylic acid with at least two carboxyls (dicarboxylic acid, tricarboxylic acid or have the more carboxylic acid of high functionality) and has at least one amino alcohol (alkanolamine) amino and at least two hydroxyls.
Suitable carboxylic acid has 2 to 4 usually, 2 or 3 carboxyls particularly, and has alkyl, aryl or the arylalkyl that contains 1 to 30 C atom.The carboxylic acid that is considered comprises all dicarboxylic acid, tricarboxylic acid and the tetracarboxylic acid of having stated at ultrabranching polyamide, and these sour derivatives.
Employed carboxylic acid is succsinic acid, pentanedioic acid, hexanodioic acid, 1 more preferably, 2-, 1,3-or 1,4-cyclohexane dicarboxylic acid, phthalic acid, m-phthalic acid, terephthalic acid or their dimethyl esters.Preferred especially succsinic acid and hexanodioic acid.
Preferred and suitable amino alcohols (alkanolamine) with at least one amino and at least two hydroxyls are dioxane hydramine and three alkanolamines.The example of operable dioxane hydramine as shown in Equation 1,
Figure GPA00001139222000331
Wherein R1, R2, R3 and R4 are hydrogen, C independently of one another 1-6Alkyl, C 3-12Cycloalkyl or C 6-14Aryl (comprising arylalkyl).
Suitable dioxane hydramine is diethanolamine, dipropanolamine, diisopropanolamine (DIPA), 2-amino-1, ammediol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, two butanolamines, two isobutyl hydramine, two (2-hydroxyl-1-butyl) amine, two (2-hydroxyl-1-propyl group) amine and two hexamethylene hydramine.
Three suitable alkanolamines as shown in Equation 2,
Figure GPA00001139222000332
Wherein R1, R2 and R3 be suc as formula 1 definition, and l, m and n are the integer of 1-12 independently of one another.Suitable example is as three (methylol) aminomethane.
Employed amino alcohol preferably includes diethanolamine (DEA) and diisopropanolamine (DIPA) (DIPA).
In a kind of preferable methods, employed carboxylic acid comprises dicarboxylic acid, and employed amino alcohol comprises the alcohol with an amino and two hydroxyls.
This method also can be used for preparing the polyesteramide of functionalization.For this reason, also use comonomer C, if they can before carboxylic acid, amino alcohol and the proper monomer M reaction, during or add afterwards.Produce a kind of polymkeric substance thus by comonomer unit and functional group's chemistry modification thereof.
Therefore, a preferred embodiment of this method is: if before carboxylic acid, amino alcohol and the proper monomer M reaction, during or afterwards, also use a kind of comonomer C, produce the polyesteramide of modification.Comonomer can comprise a kind of, two or more functional group.
Suitable comonomer C is saturated and undersaturated monocarboxylic acid, comprise lipid acid, its acid anhydrides and ester, alcohol, acrylate, and simple function mentioned above or the more alcohol of high functionality (comprising two pure and mild polyvalent alcohols), amine (comprising diamines and triamine), and amino alcohol (alkanolamine), as preamble at as described in the hyperbranched polyamines.
The amount of comonomer C depends on the degree of polymer modification usually.The amount of comonomer C is generally 0.5 weight % to 40 weight % based on employed amino alcohol and carboxylic acid monomer's total amount meter, preferred 1 weight % to 30 weight %.
The quantity (hydroxyl value) of free OH is generally 10 to 500 in the final polyesteramide product, and preferred 20 to 450mg KOH/ gram polymkeric substance can be determined by for example titration according to DIN 53240-2.
The quantity (acid number) of free COOH base is generally 0 to 400 in the final polyesteramide product, preferred 0 to 200mg KOH/ gram polymkeric substance, and can determine by the titration according to DIN 53240-2 similarly.
The reaction of carboxylic acid and amino alcohol is carried out usually at elevated temperatures, for example at 80-250 ℃, especially 90-220 ℃, carries out under 95-180 ℃.If for the purpose of modification, catalyzer (later stage in seeing below) is then used in polymkeric substance and comonomer C reaction for this reason, and temperature of reaction can be regulated according to employed catalyzer, operation is usually at 90-200 ℃, preferred 100-190 ℃, especially carries out under 110-180 ℃.
Operation preferably rare gas element as, or in a vacuum,,, carry out under the situation of 4-dioxane, dimethyl formamide (DMF) or N,N-DIMETHYLACETAMIDE (DMAc) as 1 having solvent or not having solvent.But, do not require using solvent;---be suitably under the existence of catalyzer and carry out---reaction at elevated temperatures if for example carboxylic acid can mix with amino alcohol.The water that reaction forms in polymerization (polycondensation) process is for example absorbed in a vacuum or is used suitable solvent such as toluene to remove by component distillation.
The reaction terminating of carboxylic acid and amino alcohol can be discovered by the rising rapidly of reaction mixture viscosity.When viscosity begins to raise, but termination reaction for example stops by cooling.Then, the species of mixture can be used for determining the quantity of carboxyl in (in advance) polymkeric substance, for example determine by titration, to obtain acid number according to DIN53402-2, then, if suitable, can add monomer M and/or comonomer C and react.
Pressure is unimportant usually, for example can be absolute value 1mbar to 100bar.If do not use solvent, the water in then reacting simply method is removed by operating in a vacuum, for example under absolute value 1-500mbar.Reaction times is generally 5 minutes to 48 hours, and preferred 30 minutes to 24 hours, more preferably 1 hour to 10 hours.
As mentioned above, mentioned comonomer C can before the polymerization process, during or add afterwards, to obtain the chemical modification of hyperbranched polyesteramide.
This method can be used the catalyzer of a kind of catalysis carboxylic acid and amino alcohol reaction (esterification).
Appropriate catalyst has an acidic catalyst, preferred organic catalyst, organo-metallic catalyst, perhaps enzyme.
The acid organic catalyst that can mention has sulfuric acid, phosphoric acid, phosphonic acids, Hypophosporous Acid, 50, hydrazine aluminum sulfate, alum, acidic silica gel (pH≤6, especially≤5), and acidic alumina.Other example of spendable acid organic catalyst has general formula Al (OR) 3Aluminum compound, and general formula Ti (OR) 4Titanium compound.The example of preferred acid organic catalyst is selected from dialkyl tin oxide R 2SnO, wherein R as above defines.The particularly preferred di-n-butyl stannic oxide that is represented as of acid organo-metallic catalyst can " oxotin " be buied.An example of suitable material is Fascat
Figure GPA00001139222000351
4201, it is a kind of di-n-butyl stannic oxide that derives from Atofina.
Preferred acid organic catalyst is an acidic organic compound, and it has for example phosphate, sulfonic group, sulfate or phosphonate group.Preferred especially sulfonic acid is as tosic acid.Also can use acid ion exchangers as acid organic catalyst, an example is the polystyrene resin that contains sulfonic group and use the divinyl benzene crosslinked of about 2mol%.
If the use catalyzer, it is measured based on carboxylic acid and amino alcohol total amount meter, is generally 1-5000ppm weight, preferred 10-1000ppm weight.
Particularly, the reaction of comonomer C also can come catalysis by the amidation catalyst of routine, usually 40-90 ℃, preferred 50-85 ℃, especially under 55-80 ℃, in the presence of free radical inhibitors, carry out.
Method of the present invention can preferably be carried out in mode intermittently, perhaps carry out continuously, for example in stirred vessel, tubular reactor, tower reactor or other popular response device, carry out, it can have static state or dynamic mixing tank and conventional pressure-controlling and temperature-control device, and the device that can be used for operation under the rare gas element.
For the operation of not using solvent, final product is directly acquisition usually, and if suitablely can carry out purifying via the purification process of routine.If used solvent simultaneously, then the mode that this solvent can be common after the reaction is removed cloud from reaction mixture, for example removes by vacuum distilling.
Hyperbranched polymers mentioned above can be carried out type of polymerization (polymer-analogous reaction) in addition.Can more effectively regulate its performance thus, in some cases, also can regulate its purposes in multiple dispersion.For type of polymerization, the functional group (for example group A or B) that originally was present in the polymkeric substance is reacted, so that the polymkeric substance of gained contains at least a new functional group.
The type of polymerization of hyperbranched polymer can be carried out during polymer manufacture, carries out immediately after polyreaction, perhaps carries out in independent reactions steps.
If before polymkeric substance is synthetic or during, the component that is added also contains other functional group except that containing group A and B, then product is these other functional groups hyperbranched polymers of stochastic distribution basically.
Be used for the required functional group that compound that functional group shifts (transfunctionalization) at first can comprise new introducing, and can with second kind of group of the group B reaction of employed hyperbranched polymer raw material, thereby form a key.Its example be isocyanate group and hydroxycarboxylic acid or with the reaction of aminocarboxylic acid, to form an acid functionality, the perhaps reaction of OH base and acrylic anhydride is to form a reactive acrylic double bond.
The example of the appropriate functional group that can introduce by suitable reactive component comprises, is in particular the acidity that contains the H atom or the derivative of basic group and these groups, as-OC (O) OR ,-COOH ,-COOR ,-CONHR ,-CONH 2,-OH ,-SH ,-NH 2,-NHR ,-NR 2,-SO 3H ,-SO 3R ,-NHCOOR ,-NHCONH 2,-NHCONHR etc.If suitable, also ionizable functional group can be changed into corresponding salt by suitable acid or alkali.Another kind of possibility be with primary, the second month in a season or uncle's amino is quaternized, for example quaternized with alkyl halide or dialkylsulfates.This step can be used for for example obtaining the hyperbranched polymers of water miscible or water dispersible.
The R base of described group is preferably alkyl straight or branched, that do not replace or replace.For example, it is C 1-C 30Alkyl or C 6-C 14Aryl.The example of suitable functional group is-CN or-OR a, R wherein a=H or alkyl.
Hydrophilic and hydrophobic part has specific ratio each other, and the application in dispersion is favourable for hyperbranched polymer.The hydrophobicity of hyperbranched polymer can realize by the hydrophobic polymer that for example uses simple function group, in the hydrophobic polymer of this simple function group reactive group before the polymerization, during or carry out modification afterwards.Therefore, for example, polymkeric substance of the present invention can be by with simple function group, saturated or undersaturated aliphatic series or aromatic amine, alcohol, carboxylic acid, epoxide or isocyanate reaction and hydrophobization.
In addition, also can example will contain the difunctionality of hydrophobic grouping or more the polyfunctional monomer of high functionality during molecular weight increases, introduce by copolymerization.For this purpose, can for example use difunctionality or more polyfunctional alcohol, amine, isocyanic ester, carboxylic acid and/or the epoxide of high functionality, they also have alkyl, the alkenyl or alkynyl of aromatic group or long-chain except reactive group.
This monomeric example is an alcohol, as Zerol, glyceryl monooleate, ethylene glycol, ethohexadiol, decanediol, dodecanediol, octadecandiol, dimer Fatty Alcohol(C12-C14 and C12-C18); Amine is as hexamethylene-diamine, octamethylenediamine, dodecane diamines; Isocyanic ester, as aromatics or aliphatic vulcabond and polyisocyanates, as diphenylmethanediisocyanate and more high-grade oligomer, tolylene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate, two (two isocyanato-cyclohexyl) methane or two (isocyanato-methyl) hexanaphthene; And acid, as hexanodioic acid, suberic acid, dodecanedioic acid, octadecane diacid or dimer (fatty acid) yl.
But also hydrophilization of hyperbranched polymers used according to the invention.This can be by for example will comprising hydroxyl and/or primary amino or secondary amino group hyperbranched polymer change into the polymer polyatomic alcohol of high functionality, described oxirane such as oxyethane, propylene oxide, butylene oxide ring or its mixture by reaction with oxirane.For alkoxylate, preferably use oxyethane.But also can select in addition functionality is synthetic component during epoxy alkanol (alkylene oxide alcohol) two or two or more or epoxy alkanamine (alkyleneoxide amine) prepare as hyperbranched polymer.
Also can generate hyperbranched polymer with different functionality.This can pass through, and for example realizes to carry out functional group to shift with the mixture reaction of different compounds, perhaps by the initial functional group reactions that exists of a part is realized.
Also can be used for polymeric ABC type or AB by use 2C type monomer generates the compound with mixed functionality, the functional group that C representative and A or B do not react under selected reaction conditions.
Polymeric dispersions PD)
Polymeric dispersions PD) uses at least a ethylenically unsaturated monomers (M) preparation.Monomer (M) comprises α, and β-ethylenically unsaturated monomers is purpose of the present invention, and this unsaturated monomer comprises the monomer with terminal double link.Monomer (M) preferably is selected from α, the undersaturated monocarboxylic acid of β-ethylenic and dicarboxylic acid and C 1-C 20Ester, vinyl aromatic compounds, vinyl alcohol and C that alkanol forms 1-C 30Ester, ethylenic unsaturated nitrile, vinyl halide, vinylidene halide, single ethylenic unsaturated carboxylic acid and sulfonic acid, phosphorous-containing monomers, α that monocarboxylic acid forms, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 2-C 30Ester, α that the alkane glycol forms, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and contain the C of a primary amino or secondary amino group 2-C 30Ester, α that amino alcohol forms, the primary amide of β-ethylenic unsaturated monocarboxylic and N-alkyl derivative and N, N-vinylamide compound, allyl alcohol and the C of N-dialkyl derivatives, N-vinyl lactam, open chain 1-C 30Ester, α that monocarboxylic acid forms, ester, α that β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and amino alcohol form, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and contain acid amides, the N that the diamines of at least one primary amino or secondary amino group forms, N-diallyl amine, N, nitrogen heterocyclic ring, vinyl ether, C that N-diallyl-N-alkylamine, vinyl and allyl group replace 2-C 8-monoolefine, the non-aromatic hydrocarbon with at least two conjugated double bonds, polyethers (methyl) acrylate, contain the monomer of urea groups and their mixture.
Suitable α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 1-C 20The ester that alkanol forms has (methyl) methyl acrylate, the ethylacrylic acid methyl esters, (methyl) ethyl propenoate, the ethyl propylene acetoacetic ester, (methyl) vinylformic acid n-propyl, (methyl) isobutyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, the ethyl propylene tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, the positive heptyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid 1,1,3,3-tetramethyl butyl ester, (methyl) vinylformic acid (ethyl hexyl) ester, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid n-undecane base ester, (methyl) vinylformic acid ester in three last of the ten Heavenly stems, (methyl) vinylformic acid myristin, (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid palm ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid nonadecyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid docosyl ester, (methyl) vinylformic acid tetracosyl ester, (methyl) vinylformic acid ceryl ester, (methyl) vinylformic acid triacontyl ester, (methyl) vinylformic acid palm oil base ester, (methyl) vinylformic acid oil base ester, the inferior oil base ester of (methyl) vinylformic acid, (methyl) vinylformic acid flax base ester, (methyl) stearyl acrylate base ester, (methyl) vinylformic acid Lauryl Ester, and their mixture.
Preferred vinyl aromatic compounds has vinylbenzene, 2-methyl styrene, 4-vinyl toluene, 2-(normal-butyl) vinylbenzene, 4-(normal-butyl) vinylbenzene or 2-(positive decyl) vinylbenzene, and special optimization styrene.
Suitable vinyl alcohol and C 1-C 30The ester that monocarboxylic acid forms has, for example vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester, propionate, versatic acid vinyl esters, and their mixture.
Suitable ethylenic unsaturated nitrile has vinyl cyanide, methacrylonitrile, and their mixture.
Suitable vinyl halide and vinylidene halide have vinylchlorid, Ethylene Dichloride, vinyl fluoride, difluoroethylene, and their mixture.
Suitable ethylenic unsaturated carboxylic acid, sulfonic acid and phosphonic acids or their derivative have vinylformic acid, methacrylic acid, ethylacrylic acid, α-Lv Bingxisuan, Ba Dousuan, toxilic acid, maleic anhydride, methylene-succinic acid, citraconic acid, methylfumaric acid, propene dicarboxylic acid, equisetic acid, fumaric acid, have 4-10, the inferior sour mono-methyl of the monoesters of single ethylenic unsaturated dicarboxylic acid of preferred 4-6 carbon atom such as horse, vinyl sulfonic acid, allyl sulfonic acid, vinylformic acid sulphur ethyl ester, methacrylic acid sulphur ethyl ester, vinylformic acid sulphur propyl ester, methacrylic acid sulphur propyl ester, 2-hydroxyl-3-acryloxy propanesulfonic acid, 2-hydroxy-3-methyl acryloxy propanesulfonic acid, styrene sulfonic acid and 2-acrylamide-2-methyl propane sulfonic acid.Suitable styrene sulfonic acid and derivative thereof have vinylbenzene-4-sulfonic acid and vinylbenzene-3-sulfonic acid, and their an alkali metal salt or alkaline earth salt, as vinylbenzene-3-sodium sulfonate and vinylbenzene-4-sodium sulfonate.Particularly preferred is vinylformic acid, methacrylic acid and their mixture.
The example of phosphorous-containing monomers for example has vinyl phosphonate and allyl group phosphonic acids.What other was suitable is monoesters and diester, the especially monoesters with phosphonic acids and phosphoric acid and (methyl) vinylformic acid hydroxyalkyl acrylate.What other was suitable has by an esterification of (methyl) vinylformic acid hydroxyalkyl acrylate, perhaps by a kind of different alcohol such as the phosphonic acids of alkanol esterification and the diester of phosphoric acid.Be used for the ester that suitable (methyl) vinylformic acid hydroxyalkyl acrylate of these esters has the independent monomer of following conduct specifically to list, (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 4-hydroxybutyl ester etc.Corresponding dihydrogen phosphoric acid ester monomer comprises (methyl) vinylformic acid alkyl acid phosphate (phosphoalkyl) ester, as (methyl) vinylformic acid 2-phosphoric acid ethyl ester, (methyl) vinylformic acid 2-phosphoric acid propyl diester, (methyl) vinylformic acid 3-phosphoric acid propyl diester, (methyl) vinylformic acid phosphoric acid butyl ester and (methyl) vinylformic acid 3-phosphoric acid-2-hydroxy-propyl ester.The suitable in addition ester that phosphonic acids and phosphoric acid and oxyalkylated (methyl) vinylformic acid hydroxyalkyl acrylate are arranged, example has (methyl) acrylic acid ethylene oxide condensate, as H 2C=C (H, CH 3) COO (CH 2CH 2O) nP (OH) 2And H 2C=C (H, CH 3) COO (CH 2CH 2O) nP (=O) (OH) 2, wherein n is 1-50.Other is suitable Ba Dousuan alkyl phosphate, toxilic acid alkyl phosphate, fumaric acid alkyl phosphate, (methyl) vinylformic acid phosphate dialkyl ester, Ba Dousuan phosphate dialkyl ester and phosphoric acid allyl ester.Other suitable monomers comprises the phosphorus-containing groups described in WO 99/25780 and the US 4,733,005 (including this paper in by quoting as proof).
Suitable α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 2-C 30The ester of alkane glycol has, for example vinylformic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, ethylacrylic acid 2-hydroxyethyl ester, vinylformic acid 2-hydroxy-propyl ester, methacrylic acid 2-hydroxy-propyl ester, vinylformic acid 3-hydroxy-propyl ester, methacrylic acid 3-hydroxy-propyl ester, vinylformic acid 3-hydroxybutyl ester, methacrylic acid 3-hydroxybutyl ester, vinylformic acid 4-hydroxybutyl ester, methacrylic acid 4-hydroxybutyl ester, vinylformic acid 6-hydroxyl polyhexamethylene, methacrylic acid 6-hydroxyl polyhexamethylene, vinylformic acid 3-hydroxyl-2-(ethyl hexyl) ester, methacrylic acid 3-hydroxyl-2-(ethyl hexyl) ester etc.
Suitable α, the primary amide of β-ethylenic unsaturated monocarboxylic and N-alkyl and N, the N-dialkyl derivatives has acrylamide, Methacrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-n-octyl (methyl) acrylamide, N-(1,1,3, the 3-tetramethyl butyl) (methyl) acrylamide, N-ethylhexyl (methyl) acrylamide, N-n-nonyl (methyl) acrylamide, the positive decyl of N-(methyl) acrylamide, N-n-undecane base (methyl) acrylamide, N-tridecyl (methyl) acrylamide, N-tetradecyl (methyl) acrylamide, N-pentadecyl (methyl) acrylamide, N-hexadecyl (methyl) acrylamide, N-heptadecyl (methyl) acrylamide, N-nonadecyl (methyl) acrylamide, N-dodecyl (methyl) acrylamide, N-docosyl (methyl) acrylamide, N-tetracosyl (methyl) acrylamide, N-ceryl (methyl) acrylamide, N-triacontyl (methyl) acrylamide, N-palm oil base (methyl) acrylamide, N-oil base (methyl) acrylamide, inferior oil base (methyl) acrylamide of N-, N-flax base (methyl) acrylamide, N-stearyl (methyl) acrylamide, N-lauryl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, morpholinyl (methyl) acrylamide.
Suitable N-vinyl lactam and derivative thereof have, for example N-vinyl pyrrolidone, N-vinyl piperidone, N-caprolactam, N-vinyl-5-N-methyl-2-2-pyrrolidone N-, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-hexanolactam, N-vinyl-7-ethyl-2-hexanolactam etc.
Suitable open chain N-vinylamide compound has, for example N-vinyl formamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl acetamide, N-vinyl propionic acid amide, N-vinyl-N-methyl propanamide and N-vinyl butyramide.
Suitable α, the ester that β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and amino alcohol form has (methyl) vinylformic acid N, N-dimethylaminomethyl ester, (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylaminopropyl ester, (methyl) vinylformic acid N, N-diethylamino propyl diester and (methyl) vinylformic acid N, N-dimethylamino cyclohexyl ester.
Suitable α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and contain the ester that the diamines of at least one primary amino or secondary amino group forms N-[2-(dimethylamino) ethyl arranged] acrylamide, N-[2-(dimethylamino) ethyl] Methacrylamide, N-[3-(dimethylamino) propyl group] acrylamide, N-[3-(dimethylamino) propyl group] Methacrylamide, N-[4-(dimethylamino) butyl] acrylamide, N-[4-(dimethylamino)-butyl] Methacrylamide, N-[2-(diethylamino) ethyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] acrylamide, N-[4-(dimethylamino) cyclohexyl] Methacrylamide etc.
In addition, suitable monomers M) also have N, N-diallyl amine and N, N-diallyl-N-alkylamine and their acid salt, and quaternized products.Alkyl herein is preferably C 1-C 24Alkyl.Preferred N, N-diallyl-N-methylamine and N, N-diallyl-N, N-Dimethyl Ammonium compound is as muriate and bromide.
Other suitable monomers M) nitrogen heterocyclic ring such as N-vinyl imidazole or the N-vinyl-glyoxal ethyline that has vinyl and allyl group to replace, and the heteroaryl compound of vinyl and allyl group replacement, as 2-vinyl pyridine and 4-vinylpridine, 2-allyl pyridine and 4-allyl pyridine, and their salt.
Suitable C with at least two conjugated double bonds 2-C 8Monoolefine and non-aromatic hydrocarbon have ethene, propylene, iso-butylene, different propylene, divinyl etc.
Suitable polyethers (methyl) acrylate has the compound of general formula (A),
Figure GPA00001139222000411
Wherein
The order of ethylene oxide unit is arbitrarily,
K and l are the integer of a 0-100 independently of one another, and the sum of k and l is at least 3,
R aBe hydrogen, C 1-C 30Alkyl, C 5-C 8Cycloalkyl, C 6-C 14-aryl or (C 6-C 14-) aryl-(C 1-C 4-) alkyl,
R bBe hydrogen or C 1-C 8Alkyl,
Y is O or NR c, R wherein cBe hydrogen, C 1-C 30Alkyl or C 5-C 8Cycloalkyl.
Preferably, k is the integer of a 1-100, more preferably is the integer of the integer of 3-50, especially 4-25.Preferably, l is the integer of a 1-100, more preferably is the integer of the integer of 3-50, especially 4-25.
K and l and be preferably 3-200, especially 4-100.
Preferably, the R in the formula (A) aBe hydrogen or C 1-C 18-alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, n-pentyl, n-hexyl, octyl group, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl.
Preferably, R bBe hydrogen or C 1-C 6-alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl or n-hexyl, especially hydrogen, methyl or ethyl.Particularly preferred R bBe hydrogen or methyl.
Preferably, the Y in the formula (A) is O or NH, especially O.
Suitable polyethers (methyl) acrylate is above-mentioned α, the polycondensation product of β-ethylenic unsaturated monocarboxylic and/or dicarboxylic acid or their acyl chlorides, acid amides and acid anhydrides and Aethoxy Sklerol (polyetherol).Suitable Aethoxy Sklerol can easily pass through oxyethane, 1,2 epoxy prapane and/or Epicholorohydrin and starting molecule, as water or short chain alcohol R aThe prepared in reaction of-OH.Oxirane can use separately, alternately use continuously or use with form of mixtures.Polyether acrylate can use separately or be used to prepare emulsion polymer used according to the invention with form of mixtures.
Polymeric dispersions PD) preferably include at least a polyethers (methyl) acrylate of copolymerized form, it is selected from the compound of general formula I or II or their mixture,
Figure GPA00001139222000421
Wherein
N is the integer of a 3-15, the integer of preferred 4-12,
R aBe hydrogen, C 1-C 20Alkyl, C 5-C 8Cycloalkyl or C 6-C 14Aryl,
R bBe hydrogen or methyl.
The commercially available acquisition of suitable polyethers (methyl) acrylate, it is called Bisomer for for example name
Figure GPA00001139222000422
From Laporte Performance Chemicals, the multiple product type of UK.These products comprise, for example Bisomer MPEG 350MA, it is a kind of methoxy poly (ethylene glycol) monomethacrylates (methoxypolyethylene glycol monomethacrylate).
Suitable contain the derivative that the monomeric example of urea groups is N-vinyl urea or N-allyl urea or tetrahydroglyoxaline-2-ketone.They comprise N-vinyl-tetrahydroglyoxaline-2-ketone and N-allyl imidazole quinoline-2-ketone, N-vinyloxy group ethyl imidazol(e) quinoline-2-ketone, N-(2-(methyl) acrylamide ethyl) tetrahydroglyoxaline-2-ketone, N-(2-(methyl) acryloxy ethyl) tetrahydroglyoxaline-2-ketone (being 2-urea groups (methyl) vinylformic acid), N-[2-((methyl) acryloxy acetamido) ethyl] tetrahydroglyoxaline-2-ketone etc.
The monomer that preferably contains urea groups is N-(2-acryloxy ethyl) tetrahydroglyoxaline-2-ketone and N-(2-methacryloxyethyl) tetrahydroglyoxaline-2-ketone.Preferred especially N-(2-methacryloxyethyl) tetrahydroglyoxaline-2-ketone (2-urea groups methacrylic ester, UMA).
Above-mentioned monomer M) can use separately, to use, perhaps to use with the monomeric form of mixtures of inhomogeneity with the monomeric form of mixtures of same class.
For letex polymerization, preferably use based on monomer M) gross weight counts at least 40 weight %, more preferably at least 60 weight % especially are at least a monomer M 1 of at least 80 weight %), it is selected from α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 1-C 20Ester, vinyl aromatic compounds, vinyl alcohol and C that alkanol forms 1-C 30Ester, ethylenic unsaturated nitrile, vinyl halide, vinylidene halide that monocarboxylic acid forms, and their mixture (principal monomer).Preferably, monomer M 1) being used for the amount of letex polymerization based on monomer M) the gross weight meter is up to 99.9 weight %, more preferably is up to 99.5 weight %, especially is up to 99 weight %.
Principal monomer M1) preferably be selected from:
(methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, the positive heptyl ester of (methyl) vinylformic acid, the positive heptyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) 2-EHA, vinylbenzene, 2-methyl styrene, vinyl-acetic ester, vinyl cyanide, methacrylonitrile, and their mixture.
Except that at least a principal monomer M1), be used for preparing PD) free-radical emulsion polymerization also can use at least a other monomer M 2), its common content less (secondary monomer).For letex polymerization, preferably using based on monomer M) the gross weight meter is up to 60 weight %, more preferably is up to 40 weight %, especially be up at least a monomer M 2 of 20 weight %), it is selected from the acid anhydrides of ethylenic unsaturated monocarboxylic and dicarboxylic acid and ethylenic unsaturated dicarboxylic acid and half ester (halbestern), ethylenic unsaturated sulfonic acid, (methyl) acrylamide, C 1-C 10(methyl) vinylformic acid hydroxyalkyl acrylate, C 1-C 10Hydroxyalkyl (methyl) acrylamide, and their mixture.Preferably, monomer M 2) if---existence---amount that is used for letex polymerization is based on monomer M) gross weight counts at least 0.01 weight %, more preferably at least 0.05 weight %, especially at least 0.1 weight %, at least 0.5 weight % particularly, at least 1 weight % more especially is all based on monomer M) total restatement.
For letex polymerization, especially preferably use 0.1 weight % to 60 weight %, preferred 0.5 weight %-40 weight %, the especially at least a monomer M 2 of 1 weight %-20 weight %).First kind monomer M 2) comprises at least a monomer that has acid groups, preferably be selected from the unsaturated C of single ethylenic 3-C 8Monocarboxylic acid, the unsaturated C of single ethylenic 4-C 8Dicarboxylic acid, their acid anhydrides and half ester, single ethylenic unsaturated sulfonic acid and their mixture.The monomer M 2 that contains acid groups) content of (if having this monomer) is based on monomer M) the gross weight meter be preferably 0.05 weight %-15 weight %, 0.1 weight %-10 weight % more preferably.The second class monomer M 2) comprise at least a neutral list ethylenically unsaturated monomers, it preferably is selected from the unsaturated C of single ethylenic 3-C 8The acid amides of monocarboxylic acid, the unsaturated C of single ethylenic 3-C 8Hydroxyl-the C of monocarboxylic acid 2-C 4Alkyl ester, and their mixture.Neutral monomer M2) content of (if having this monomer) is based on monomer M) the gross weight meter be preferably 0.01 weight %-15 weight %, 0.1 weight %-10 weight % more preferably.The 3rd class monomer M 2) comprises at least a monomer of acid groups and the mixture of at least a neutral list ethylenically unsaturated monomers of having.These monomer M 2) summation is based on monomer M) the gross weight meter be preferably 0.1 weight %-20 weight %, 0.5 weight %-15 weight % more preferably.Monomer M 2) especially be selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, fumaric acid, maleic anhydride, acrylamide, Methacrylamide, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl Methacrylamide, and their mixture.
The example of the binding substances specially suitable principal monomer M1 that is used for the inventive method) is as follows:
N-butyl acrylate, methyl methacrylate;
N-butyl acrylate, methyl methacrylate, vinylbenzene;
N-butyl acrylate, vinylbenzene;
N-butyl acrylate, EHA;
N-butyl acrylate, EHA, vinylbenzene.
Above-mentioned particularly preferred principal monomer M1) binding substances can with specially suitable monomer M 2) combine described monomer M 2) preferably be selected from vinylformic acid, methacrylic acid, acrylamide, Methacrylamide and their mixture.
In a specific embodiments, be used for preparing PD) free-radical emulsion polymerization except that M1) and if---existence---M2), also can use at least a polyethers (methyl) acrylate.This polyethers (methyl) acrylate is preferably with based on monomer M) total restatement be no more than 25 weight %, use more preferably no more than the amount of 20 weight %.For letex polymerization, especially preferably use at least a polyethers (methyl) acrylate of 0.1 weight %-20 weight %, preferred 1 weight %-15 weight %.Suitable polyethers (methyl) acrylate be mentioned above those.Preferably, polyethers (methyl) acrylate is selected from the compound of general formula I or II or their mixture,
N is the integer of a 3-15, the integer of preferred 4-12,
R aBe hydrogen, C 1-C 20Alkyl, C 5-C 8Cycloalkyl or C 6-C 14Aryl,
R bBe hydrogen or methyl.
In a specific embodiment, be used to prepare PD) free-radical emulsion polymerization except that M1) and if---existence---M2) and/or polyethers (methyl) acrylate, use at least a monomer that contains urea groups to carry out.This urea functional group monomer is based on monomer M) the gross weight meter preferably being no more than 25 weight %, use more preferably no more than the amount of 20 weight %.For letex polymerization, especially preferably use 0.1 weight % to being no more than 20 weight %, more preferably using at least a monomer that contains urea groups of 1 weight %-15 weight %.The suitable monomer that contains urea groups is those that above specifically list.When preparation polymeric dispersions of the present invention, except that aforementioned monomer M), also can use at least a linking agent.Monomer with crosslinking functionality is the compound that has at least two polymerisable, unsaturated unconjugated double bonds of ethylenic in the molecule.Crosslinked also can, for example take place by photochemical activity.For this purpose, be preparation PD) but at least a monomer that contains the group of photoactivation also can be used.Light trigger also can add in addition.Linking agent also can realize that this functional group can carry out chemical crosslink reaction with complementary functional group by for example such functional group.In this case, the complementary group all can be connected on the emulsion compound.Crosslinked for carrying out, can use a kind of linking agent, it can carry out chemical crosslink reaction with the functional group of emulsion polymer.
Suitable crosslinking agent has, for example acrylate, methacrylic ester, the allyl ester or the vinyl ester of dihydroxy alcohol at least.The hydroxyl of parent alcohol is esterification or partial esterification fully; But linking agent comprises at least two ethylenic unsaturated groups.
The example of parent alcohol has dihydroxy alcohol, as 1,1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 2, the 3-butyleneglycol, 1, the 4-butyleneglycol, but-2-ene-1, the 4-glycol, 1, the 2-pentanediol, 1, the 5-pentanediol, 1, the 2-hexylene glycol, 1, the 6-hexylene glycol, decamethylene-glycol, 1, the 2-dodecanediol, 1, the 12-dodecanediol, neopentyl glycol, 3-methylpent-1, the 5-glycol, 2,5-dimethyl-1,3-hexylene glycol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 1, the 2-cyclohexanediol, 1, the 4-cyclohexanediol, 1, two (hydroxymethyl) hexanaphthenes of 4-, hydroxy new pentane acid neopentyl glycol monoesters, 2, two (4-hydroxy phenyl) propane of 2-, 2, two [4-(2-hydroxypropyl) phenyl] propane of 2-, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, 3 third glycol, 4 third glycol, 3-thiapentane-1,5-glycol, and polyoxyethylene glycol, polypropylene glycol and polytetrahydrofuran, its molecular weight separately is 200-10 000.Except that the homopolymer of oxyethane or propylene oxide, also can use the segmented copolymer of oxyethane or propylene oxide.Example with parent alcohol of two above hydroxyls has TriMethylolPropane(TMP), glycerine, tetramethylolmethane, 1,2,5-penta triol, 1,2,6-hexanetriol, cyanuric acid, sorbitanic, carbohydrate such as sucrose, glucose and seminose.Certainly after also can using with oxyethane or propylene oxide reaction polyhydroxy-alcohol as corresponding ethoxylate or propoxylation thing.Polyhydroxy-alcohol also can be at first by changing into corresponding glycidyl ether with the Epicholorohydrin reaction.
Other suitable crosslinking agent is vinyl ester or monohydroxy unsaturated alcohol and the unsaturated C of ethylenic 3-C 6The ester that carboxylic acid forms, the example of described acid is vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or fumaric acid.The example of this alcohol has vinyl carbinol, 1-butylene-3-alcohol, 5-hexen-1-ol, 1-octene-3-alcohol, 9-decen-1-ol, two cyclopentenols (dicyclopentenyl alcohol), 10-undecene-1-alcohol, styryl carbinol, geraniol, crotyl alcohol or suitable-9-vaccenic acid-1-alcohol.Another selection is that the example of described polycarboxylic acid is propanedioic acid, tartrate, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succsinic acid with the undersaturated alcohol polycarboxylic acid esterification of monohydroxy.
Other suitable crosslinking agent is the ester of unsaturated carboxylic acid and above-described polyhydroxy-alcohol, and example has the ester of oleic acid, Ba Dousuan, styracin or undecylenic acid and above-described polyhydroxy-alcohol.
In addition, suitable crosslinking agent be have at least two two keys straight or branched, line style or cyclic, non-aliphatic series or aromatic hydrocarbon, for aliphatic hydrocrbon, it must be unconjugated, example is divinylbenzene, divinyl toluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-tetrahydrobenzene, trivinyl tetrahydrobenzene or molecular weight are the polyhutadiene of 200-20000.
Other suitable crosslinking agent is acrylamide, Methacrylamide and dual functional at least amine N-allyl amine.This amine is, 1,1 for example, 3-diaminopropanes, 1, the basic alkane of 4-diamino, 1,6 diamino hexane, 1,12-dodecane diamines, piperazine, diethylenetriamine or isophorone diamine.Similarly, the suitable acid amides that forms by allyl amine and unsaturated carboxylic acid in addition, the carboxylic acid of described carboxylic acid such as vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or aforesaid binary at least.
In addition, triallylamine and triallyl monoalkyl ammonium salt are as triallyl ammonio methacrylate or the also suitable linking agent of doing of triallyl methyl ammonium sulfate.
The suitable N-vinyl compound that also has urea derivatives, at least dual functional acid amides, cyanurate or urethane are as urea, ethylene urea, propylene urea or tartramide (tartaramide), for example N, N '-divinyl ethylene urea or N, N '-divinyl propylene urea.
Other suitable crosslinking agent has divinyl diox, tetraallyl silane or tetrem thiazolinyl silane.Should understand the mixture that also can use aforesaid compound.The preferred water-soluble cross-linker that uses.
In addition, cross-linking monomer comprises that also those also contain the monomer of reactive functional groups except that the ethylenic unsaturated double-bond, described reactive functional groups such as aldehyde radical, ketone group or Oxyranyle, and can react with the linking agent that is added.But ketone group or the aldehyde radical preferably ethylenically unsaturated compounds by copolymerization and ketone group or aldehyde radical copolymerization are connected to polymkeric substance.Suitable this compound is the vinyl alkyl ketone that has individual, preferred 1-10 the carbon atom of 1-20 in propenal, Methylacrylaldehyde, the alkyl; formyl radical vinylbenzene; has (methyl) alkyl acrylate that has an aldehyde radical and a ketone group in (methyl) alkyl acrylate of one or two ketone group or aldehyde radical or the alkyl; described alkyl preferably includes and amounts to 3-20 carbon atom, and example is as DE-A-2722097 described (methyl) acryloxyalkyl propionic aldehyde.In addition, suitable N-oxoalkyl group (methyl) acrylamide that also has known class is as by known among US-A-4226007, DE-A-2061213 or the DE-A-2207209.Particularly preferred is acetoacetyl (methyl) vinylformic acid, acetoacetoxy groups ethyl (methyl) vinylformic acid, more preferably is diacetone acrylamide.Linking agent is preferably a kind ofly can have at least two functional groups, especially two compounds to five functional groups with functional group's (especially ketone group or aldehyde radical) of polymkeric substance reacts.Be used for comprising, for example hydrazides, azanol or oxime ether or amino with the crosslinked functional group of ketone group or aldehyde radical.Suitable hydrazide compound is that for example molecular weight is no more than the poly carboxylic acid hydrazides of 500g/mol.Particularly preferred hydrazide compound is the dicarboxyl acid dihydrazide (dicarboxylic dihydrazide) with preferred 2-10 carbon atom.Their example comprises oxalic acid two hydrazides, propanedioic acid two hydrazides, amber acid dihydrazide, pentanedioic acid two hydrazides, adipic dihydrazide, sebacic dihydrazide, Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides and/or isophthalic dihydrazide.Particularly advantageous is to be adipic dihydrazide, sebacic dihydrazide and isophthalic dihydrazide.The suitable compound with azanol or oxime ether is for for example at described in the WO 93/25588 those.
By hydrotropisms's polymeric dispersions PD) in suitably add additive (additization), also can produce surface-crosslinked in addition.The adding of this additive comprises, for example adds light trigger or siccative.Suitable light trigger is by the light trigger of sunlight hits, and example has the benzophenone or derivatives thereof.Suitable siccative is for recommending to be used for the metallic compound of aqueous alkide resin, they for example based on Co or Mn ( In U.Poth Polyester und Alkydharze is after VincentzNetwork 2005, the 183 reaches).
Linked is preferably based on and is used for that the monomeric gross weight of polymeric (comprising linking agent) is counted 0.0005 weight %-5 weight %0.0005 weight %-5 weight %, more preferably the amount of 0.001 weight %-2.5 weight %, especially 0.01 weight %-1.5 weight % is used.
In a specific embodiment, letex polymerization is used based on gross weight meter 98 weight % that can polymeric compounds, more preferably at least 99 weight %, especially at least 99.5 weight %, particularly single ethylenically unsaturated compounds of 100 weight % at least.
A specific embodiment is polymeric dispersions PD) do not comprise the linking agent of copolymerization.
Monomer mixture M) radical polymerization can be carried out in the presence of at least a conditioning agent.The usage quantity of conditioning agent is counted at least 0.0005 weight %-5 weight %/more preferably 0.001 weight %-2.5 weight %, especially 0.01 weight %-1.5 weight % based on being used for the monomeric gross weight of polymeric.
Conditioning agent (polymerization regulator) is the general name with compounds of high transfer constant.Conditioning agent accelerating chain shift reaction so that the polymerization degree of resulting polymers reduces, and can not influence overall reaction rates.
Conditioning agent can be divided into simple function, difunctionality or multifunctional conditioning agent according to the number of functional group in the molecule, and they can cause one or more chain transfer reactions.Suitable conditioning agent for example is described in detail in J.Brandrup by K.C.Berger and G.Brandrup, E.H.Immergut, Polymer Handbook, 3 RdEd., John Wiley ﹠amp; Sons, New York, 1989, among the p.II/81-II/141.
The example of suitable conditioning agent comprises aldehydes, as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde-n and isobutyric aldehyde.
Other spendable conditioning agent is: formic acid and salt thereof or ester, and as ammonium formiate, 2,5-phenylbenzene-1-hexene, sulfovinic acid ammonium and hydroxyl ammonium phosphate.
Other suitable conditioning agent has halogen compounds, and example has alkyl halide, as tetrachloromethane, chloroform, bromo-trichloromethane, bromofom, allyl bromide 98 and benzylated title compound, as phenmethyl chlorine or phenmethyl bromine.
Other suitable conditioning agent has allylic cpd, as vinyl carbinol, functionalized allyl ethers, as allyl group ethoxylate, alkyl allyl ethers or allylin.
Preferably use the compound that contains sulphur in the combining form as conditioning agent.
The example of this compounds is inorganic bisulfites, pyrosulfite (disulfite) and hyposulfite; Perhaps organic sulfide, disulphide, polysulfide, sulfoxide and sulfone.They comprise di-n-butyl thioether, di-n-octyl thioether, diphenylsulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide ether, 20 butyl disulfides, di-n-hexyl disulfide, diacetyl disulfide, di-alcohol thioether (diethanol sulfide), di-t-butyl trithioether, dimethyl sulfoxide (DMSO), dialkyl sulfide, dialkyl group disulfide and/or diaryl sulfide.
Suitable polymerization regulator also comprises mercaptan (contain the compound of sulphur with the form of SH base, be also referred to as mercaptan).Preferential conditioning agent is single mercaptan, two mercaptan and polyfunctional mercaptan, mercaptoalcohol and/or mercaptan carboxylic acid.These examples for compounds have allyl sulfydryl acetate, ethyl thioglycolate salt, halfcystine, 2 mercapto ethanol, 1,3-mercaprol, 3-sulfydryl the third-1,2-glycol, 1,4-Mercaptobutanol, Thiovanic acid, 3-thiohydracrylic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid, thiocarbamide and alkyl sulfhydryl are as normal-butyl mercaptan, n-hexyl mercaptan or lauryl mercaptan.
The example that two sense conditioning agents---comprise two sulphur atoms that are in type of attachment---has dual functional thio-alcohol (thiol), as dimercaptopropane sulphonate (sodium salt), dimercaptosuccinic acid(DMSA), dimercapto-1-propyl alcohol, dimercaptoethane, dimercaptopropane, dimercapto butane, dimercapto pentane, dimercapto hexane, glycol dimercaptoacetate.The example of multifunctional conditioning agent has and comprises the compound that is in the sulphur atom of type of attachment more than two.The example is trifunctional and four functional mercaptan.
All above-mentioned conditioning agents can be used alone or in conjunction with each other.Specific embodiment relates to by free-radical emulsion polymerization and adds the polymeric dispersions PD that conditioning agent prepares.
Be the preparation polymkeric substance, can be by the initiator that forms free radical with monomer polymerization.
Initiator as radical polymerization; can adopt routine to be used for the peralcohol and/or the azo-compound of this purpose; example has basic metal or peroxo disulfate acid ammonium; diacetyl peroxide; dibenzoyl peroxide; succinyl peroxide; ditertiary butyl peroxide; tertiary butyl peroxybenzoic acid; cross the PIVALIC ACID CRUDE (25) tert-butyl ester; t-butyl peroxy-2-ethylhexanoate; tert butyl permaleic acid; cumene hydroperoxide; peroxidation diamino acid diisopropyl ester; two (toluoyl base) superoxide; didecanoyl peroxide; dioctanoyl peroxide; dilauroyl peroxide; t-butylperoxy isobutylate; t-butyl peroxy-acetate; two t-amyl peroxy things; tertbutyl peroxide; Diisopropyl azodicarboxylate; 2,2 '-two (2-amidine propane) dihydrochlorides of azo or 2-2 '-azo-two-(2-methyl-butyronitrile).The mixture of these initiators also is suitable for.
Also can use reducing/oxidizing (being redox) initiator system as initiator.Redox initiation system is made up of the oxygenant of at least a, normally inorganic reductive agent and a kind of organic or inorganic.Oxidation component comprises, for example the initiator of above having specifically noted at letex polymerization.For reduction components, described composition comprises, the an alkali metal salt of sulfurous acid for example, as S-WAT, sodium bisulfite, the an alkali metal salt of pyrosulphite such as Sodium Pyrosulfite, the bisulfite salt compound such as the acetone sodium bisulfite of aliphatic aldehyde and ketone, or reductive agent such as hydroxyl methane-sulfinic acid and salt or anti-bad hematic acid.Redox initiation system can use with the soluble metal compound, and described metal component of toppling over thing can exist with multiple valence state.Common redox initiation system is, for example xitix/ferric sulfate (II)/peroxidation sodium pyrosulfate, tertbutyl peroxide/sodium pyrosulfate, tertbutyl peroxide/sodium hydroxymethanesulfinate.Independent component---as reduction components---also can be mixture, for example is the sodium salt of methylol-sulfinic acid and the mixture of sodium pyrosulfate.
The amount of initiator is generally 0.1 weight %-10 weight %, preferred 0.1 weight %-5 weight % based on the total amount meter for the treatment of polymerization single polymerization monomer.Also can use two or more different initiators in the letex polymerization.
The preparation of polymeric dispersions is carried out in the presence of at least a surface active cpd usually.Detailed description to suitable protective colloid can be referring to Houben-Weyl, Methoden derorganischen Chemie, XIV/1 volume, Makromolekulare Stoffe, Georg ThiemeVerlag, Stuttgart, 1961, the 411-420 pages or leaves.Suitable emulsifying agent also can be referring to Houben-Weyl, Methoden der organischen Chemie, the 14/1st volume, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, the 192-208.
Suitable emulsifying agent is anionic, cationic and nonionic emulsifier.The preferred emulsifying agent that uses is as surfactant, and the relative molecular weight of described emulsifying agent is usually less than the molecular weight of protective colloid.More specifically, proved and only used anionic emulsifier that the binding substances that perhaps uses at least a anionic emulsifier and at least a nonionic emulsifier is suitable.
Spendable nonionic emulsifier is the nonionic emulsifier of araliphatic or aliphatic series, and example has the monoalkyl phenol of ethoxylation, two alkylphenol and trialkyl phenol (EO degree: 3-50; Alkyl: C 4-C 10), the long-chain alcohol of ethoxylation (EO degree: 3-100; Alkyl: C 8-C 36) and the homopolymer and the multipolymer of ethylene oxide/propylene oxide.They can comprise the copolymerization epoxy alkane unit of stochastic distribution or block form.Most suitable has, for example the EO/PO segmented copolymer.Preferred ethoxylate (the alkyl C that uses long chain alkanol 1-C 30, average degree of ethoxylation is 5-100), wherein, especially preferably have C 12-C 20Linear alkyl and average degree of ethoxylation are the long chain alkanol ethoxylate of 10-50; And the monoalkyl phenol of ethoxylation.
The example of suitable anionic emulsifier has alkyl sodium sulfate ester (alkyl: C 8-C 22) an alkali metal salt and ammonium salt, ethoxylation alkanol (EO degree: 2-50; Alkyl: C 12-C 18) and ethoxylated alkylphenol (EO degree: 3-50; Alkyl: C 4-C 9) an alkali metal salt and the ammonium salt of sulfuric acid monoester, alkylsulphonic acid (alkyl: C 12-C 18) an alkali metal salt and ammonium salt and alkyl aryl sulphonic acid (alkyl: C 9-C 18) an alkali metal salt and ammonium salt.Other suitable emulsifying agent can be referring to Houben-Weyl, Methoden der organischen Chemie, XIV/1 volume, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, the 192-208 pages or leaves.Similarly, suitable anionic emulsifier has two (phenylbenzimidazole sulfonic acid) ethers and/or its alkali metal salts or ammonium salt, and they have a C on one or two aromatic ring 4-C 24Alkyl.These compounds are by for example US-A-4, and 269,749 is known, and commercially available acquisition, for example with Dowfax
Figure GPA00001139222000511
The form of 2A1 (Dow Chemical Company) obtains.
Suitable cationic emulsifier is preferably quaternary ammonium halide, for example trimethylammonium cetyl chloride ammonium, methyl trioctylphosphine ammonium chloride, benzyltriethylammoinium chloride or N-C 6-C 20Alkyl pyridine, N-C 6-C 20-morpholine or N-C 6-C 20The quaternary compound of-imidazoles.
The amount of emulsifying agent is generally about 0.01 weight %-10 weight % based on the amount meter for the treatment of polymerization single polymerization monomer, preferred 0.1 weight %-5 weight %.
In addition, polymeric dispersions PD) can mix with common auxiliary agent and additive.These auxiliary agents and additive comprise, for example pH regulator agent, reductive agent and SYNTHETIC OPTICAL WHITNER, as an alkali metal salt of methylol-sulfinic acid (as Rongalit available from BASF Aktiengesellschaft
Figure GPA00001139222000512
C), complexing agent, reodorant, spices (flavor), taste-additive and viscosity modifier, alcohol for example is as glycerine, methyl alcohol, ethanol, the trimethyl carbinol, glycol etc.These auxiliary agents and additive can add in a kind of material of initial charge in the polymeric dispersions, perhaps finish the back in polymerization and add in the polymeric dispersions.
Polymerization usually 0-150 ℃, preferred 20-100 ℃, more preferably carry out under 30-95 ℃ the temperature.Polymerization is preferentially carried out under barometric point, also is feasible but carry out polymerization under elevated pressure, for example carries out under the autogenous pressure that is used for the polymeric component.In a suitable embodiment, be aggregated at least a rare gas element, as carrying out under the existence of nitrogen or argon gas.
Polymerisation medium can be made up of water separately, perhaps is made up of the mixture of water and liquid (as methyl alcohol) that can be miscible with water.Preferably only make water.Letex polymerization can periodical operation or the charging method carry out, comprise stage or gradient steps.The preferred feedstock method, wherein a part of polymerization batches or a kind of polymer feed add as initial charge, and be heated to polymerization temperature and begin polymerization, (the normally charging of separating on two or more spaces of remaining then polymerization batches, wherein one or more comprise the monomer of pure monomer or emulsification form) provided to the zone of convergency by the stack of continuous, stage or concentration gradient, keep polymerization simultaneously.
Those skilled in the art should be interpreted as term " seed polymer " a kind of finely divided polymkeric substance of aqueous polymer dispersions form.The weight average particle diameter of seed polymer (weight average, d 50) usually less than 200nm, usually in the scope of 10-150nm.The monomer composition of seed polymer is inessential usually.Be not only mainly most suitable by vi-ny l aromatic monomers, especially vinylbenzene (being known as the vinylbenzene kind) synthetic seed polymer, and mainly by vinylformic acid C 1-C 10Alkyl ester and/or methacrylic acid C 1-C 10Alkyl ester (as by butyl acrylate and methyl methacrylate) synthetic seed polymer is also most suitable.Except that these account for the principal monomer of at least 80 weight %, especially at least 90 weight % of seed polymer usually, seed polymer also can comprise and is different from above-mentioned these the monomer of copolymerized form, especially the monomer that has the solubleness of increase in water, example have monomer with at least one acid groups and/or the neutral monomer that has the solubleness of increase in water.The monomeric content of this class is no more than 20 weight % usually, especially is no more than 10 weight %, and if have this class monomer, then its content is generally 0.1 weight %-10 weight %, based on the total amount meter of the compositing monomer of seed polymer.
In the free radical aqueous emulsion polymerization process, the mode that initiator adds in the aggregation container is that those of ordinary skills are known.They can be included in the initial charge and to add in the aggregation container, and are perhaps stage or use according to its wear rate continuously in free radical aqueous emulsion polymeric process.Any situation is all carried out in the known mode of those of ordinary skills according to initiator system and polymerization temperature.Preferably, a part is comprised in the initial charge, and remainder is provided in the zone of convergency according to its wear rate.
After converging operation, the dispersion that forms in the polymerization can be carried out physics or chemical after-treatment reason.The example of this technology is known for the residual monomer reduction, for example: carry out aftertreatment by the mixture that adds polymerization starter or two or more polymerization starters under suitable temperature; Carry out the aftertreatment of polymers soln by water vapor or ammonium steam; Perhaps carry and heating up in a steamer with rare gas element; Perhaps with oxidising agent or reduction agent treated reaction mixture; Adsorption technology, as with impurity absorption at selected medium, as gac on; Perhaps carry out ultrafiltration.
Aqueous polymer dispersions PD) solids content that has is usually counted 20 weight %-70 weight % based on polymeric dispersions (comprising the highly branched polymkeric substance that is added), preferred 40 weight %-65 weight %.In a specific embodiment, solids content is at least 50 weight %, more particularly is at least 55 weight % even more particularly be at least 58 weight %.Based on aqueous polymer dispersions (comprising the highly branched polymkeric substance that is added) meter, the solids content of at least 60 weight % even at least 65 weight % also is feasible.
The second-order transition temperature T of the emulsion polymer that exists in the polymeric dispersions gPreferably, be more preferably less than 40 ℃, especially less than 30 ℃ less than 50 ℃.
The aqueous polymer dispersions PD of gained) can form itself use, perhaps use, as the binder composition in the water-borne coatings (as paint or varnish mixture) with the form of the mixture that---is generally film-forming polymer---with other polymkeric substance.
The present invention also provides a kind of coating of waterborne compositions form, and this waterborne compositions comprises at least a PD of dispersion as defined above), it comprises that a kind of highly branched polymkeric substance is as additive.Highly branched polymkeric substance also can add in the coating with a kind of form of additive.
Except that polymeric dispersions PD), the binder composition of coating also can comprise at least a other film-forming polymer.Comprising, Synolac for example.The example of suitable Synolac has water soluble alkyd resin, and it has the weight-average molecular weight of 5 000-40 000.In addition, weight-average molecular weight greater than 40 000, also be suitable greater than 100 000 Synolac especially.Synolac is a kind of by the polyethers of siccative oil, lipid acid or analogue esterification (U.Poth, P0lyester und Alkydharze, Vincentz Network 2005).Suitable water soluble alkyd resin is the Synolac with sufficiently high acid number, and acid number is preferably in the scope of 30-65mg KOH/g.Can be partially or completely neutral form if these Synolac are suitable.Weight-average molecular weight preferentially is 8000 to 35 000, more preferably is 110 000 to 35 000.
This class other film-forming polymer, particularly Synolac that use can increase the VOC content of coating are not preferred.Therefore, preferably a kind of like this coating, it comprises at least a dispersion PD) and at least a highly branched polymkeric substance, but do not comprise the film-forming polymer that is different from beyond the emulsion polymer that exists in the polymeric dispersions.
Binder composition of the present invention preferably uses with the form of water-borne coatings.The form of these coating is for example uncoloured system (varnish) or painted system.The content of pigment can be described by pigment volume concentration (PVC) (PVC).PVC has described pigment (V P) and weighting agent (V F) volume and cumulative volume---by tackiness agent (V B), the cumulative volume of the weighting agent of pigment and dry coating forms---between per-cent: PVC=(V P+ V F) * 100/ (V P+ V F+ V B).Coating can be divided into following several based on PVC:
Highly-filled interior paint, waterproof, white/unglazed about 85
Interior paint, anti-wiping, white/unglazed about 80
Semi-gloss paint, silk-matt about 35
Semi-gloss paint, mercerising about 25
The about 15-25 of high lac varnish
The external application masonry paint, the about 45-55 of white
Varnish 0
The present invention also provides a kind of coating of waterborne compositions form, and it comprises:
-at least a the PD of dispersion as defined above), it comprises highly branched polymkeric substance as a kind of additive,
If-suitable, at least a mineral filler and/or at least a mineral dye,
If-suitable, at least a common auxiliary agent, and
-water.
Preferably a kind of like this coating, it comprises:
-based on solids content, at least a polymeric dispersions as defined above of 10 weight %-60 weight %,
Mineral filler and/or the mineral dye of-10 weight %-70 weight %,
The common auxiliary agent of-0.1 weight %-20 weight %, and
-add water to 100 weight %.
PD) content that accounts for above-mentioned coating is based on solid, and promptly emulsion polymer and one or more highly branched polymkeric substance do not comprise water.
The coating of waterborne compositions form of the present invention uses preferably as coating.A scheme of the present invention relates to the coating of varnish form.Another embodiment of the invention comprises the coating of emulsion paint form.Pigmented coating of the present invention is preferably water-based semi-gloss paint or high lac varnish form.
Set forth hereinafter a kind of composition of common emulsion paint form.Emulsion paint generally includes the volatile constituent of 30 weight %-75 weight %, preferred 40 weight %-65 weight %.They are meant all the components in addition that dewaters in the preparation, are at least for example total amount of tackiness agent, filler, pigment, low voc solvent (boiling point is higher than 220 ℃), softening agent.Wherein have and be roughly:
A) 3 weight %-90 weight %, the especially finely divided polymeric dispersions PD of 10 weight %-60 weight %),
B) 0 weight %-85 weight %, preferred 5 weight %-60 weight %, the especially at least a mineral dye of 10 weight %-50 weight %,
C) 0 weight %-85 weight %, the especially mineral filler of 5 weight %-60 weight %, and
D) 0.1 weight %-40 weight %, the especially common auxiliary agent of 0.5 weight %-20 weight %.
Polymeric dispersions of the present invention more preferably is applicable to the preparation high gloss emulsion paint.The feature of these lacquers normally pigment volume concentration (PVC) PVC in the scope of 12 weight %-30 weight %.But polymeric dispersions of the present invention also particularly suitable is made masonry paint or PVC the interior paint 65-80 scope in of PVC in the 30-65 scope.Pigment volume concentration (PVC) PVC is meant the ratio of the cumulative volume of the pigment that multiply by after 100 and filler cumulative volume and pigment, filler and binder polymer; Referring to Ullmann ' s
Figure GPA00001139222000551
Der technischen Chemie, the 4th edition, the 15th volume, the 667th page.
Term " pigment " is widely used for being meant all pigment and filler in the text of the present invention that the example is colored pigment, white pigment and mineral filler.They comprise inorganic white pigment, as titanium dioxide (titanium dioxide of preferred rutile form), barium sulfate, zinc oxide, zinc sulphide white lead carbonate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, lithopone (zinc sulphide+barium sulfate); Perhaps colored pigment, example has ferric oxide, carbon black, graphite, manganese violet, prussian blue or urania green.Except that mineral dye, emulsion paint of the present invention also can comprise inorganic colored pigment, example has sepia, gamboge, pigment brown, toluidine red, p-nitroaniline red, organic yellow, indigo, azoic dyestuff, anthraquinone dye and indigoide colors, and dioxazines, quinacridone, phthalein green grass or young crops, isoindolinone, and metal complex pigment.Suitable has gas enclosure in addition to increase the synthetic white pigment of scattering of light, as Rhopaque Dispersion.
Appropriate filler has, and aluminosilicate for example is as feldspar; Silicate is as kaolin, talcum, mica, magnesite; Alkaline earth metal carbonate, as lime carbonate, its form such as calcite or chalk, magnesiumcarbonate, rhombspar; Alkaline earth metal sulphate is as calcium sulfate, silicon-dioxide etc.Yes in coating for finely divided filler preferably.Filler can be used as independent component and uses.But in practice, it is specially suitable that filler mixture has been proved to be, and example has lime carbonate/kaolin and lime carbonate/talcum.Gloss paint only comprises a spot of superfine dispersive filler usually, does not perhaps comprise filler.
Finely divided filler also can be used for the use that increases opacifying power and/or be used to save white pigment.Be to regulate the trial of opacifying power, color harmony color, preferably use colored pigment and blend filler.
As mentioned above, the content of pigment can pass through pigment volume concentration (PVC) (PVC) description.For example, the PVC of the coating of gloss form of the present invention is in the scope of 12 weight %-35 weight %, preferred 15 weight %-30 weight %.
Coating of the present invention (sofa coating) is except that polymeric dispersions PD) also can comprise at least a highly branched polymkeric substance as additive, and if suitable other film-forming polymer and pigment and other auxiliary agent of also comprising.
Except that emulsifying agent, the common auxiliary agent that is used for polymerization comprises wetting agent or dispersion agent, as trisodium phosphate, potassium pyrophosphate or ammonium pyrophosphate; Acrylic copolymer or copolymer-maleic anhydride an alkali metal salt and ammonium salt; Polyphosphonates, as 1-hydroxyl ethane-1, the 1-diphosphate sodium; And the salt of naphthene sulfonic acid, especially its sodium salt.
Other proper auxiliary agent has flowing regulator, defoamer, biocide and thickening material.Suitable thickening has, and associative thickener for example is as polyurethane thickener.The amount of thickening material preferably is less than 1 weight %, more preferably is less than 0.6 weight %, the solid content meter of coating based.
Thereby lacquer of the present invention is by preparing component in known manner in the mixing device blend that routine is used for this purpose.Find,, just polymer binder---is generally aqueous polymer dispersion---afterwards and mixes with pigment paste or pigment dispersion if by pigment, water with---suitable---auxiliary agent prepares the water-based paste or dispersion is suitable.
Usually, enamel-cover of the present invention is drawn together the nonvolatile element of 30 weight %-75 weight %, preferred 40 weight %-65 weight %.They are meant the solid content meter based on lacquer, and all components of the preparation beyond dewatering is at least the total amount of tackiness agent, pigment and auxiliary agent.Volatile constituent is mainly water.
Suitable lacquer is high lac varnish.The gloss of lacquer can be determined by DIN 67530.In this case, coating is coated on the sheet glass so that the seam of 240 μ m is wide, and at room temperature dry 72 hours.Sample is inserted in the reflexometer of calibration, and determines that the light that returns is reflected or the degree of scattering under the input angle that limits.Determined reflectometer value is that of glossiness measures (this value is high more, and glossiness is high more).
The glossiness of high lac varnish is preferably more than 60 under 20 °, and at 60 ° greater than 80.Reflectometer value is measured down at 23 ℃, and the dimensionless parameters report to change with input angle, promptly is 40 under 20 °.
Lacquer of the present invention can be applied on the base material in common mode, for example is coated with, sprays, dipping, roller coat, blade coating etc.
Preferably, it uses as building coating, promptly is used to apply buildings or building components.Described base material can be mineral substrates, as bottom ash (render), gypsum, plasterboard, masonry or concrete, timber, wood based material, metal or paper (as wallpaper) or plastics (as PVC).
Preferably, lacquer is used to the skewer of buildings, as the inboard of interior wall, door, lath, handrail, furniture etc.
The characteristics of lacquer of the present invention are easy handling, have good processing characteristics and high covering power.It is low that it pollutes content.They have good performance, as high water-repellancy, good wet sticking power (especially also at Synolac), high resistance to blocking, good recoatability, and the good fluidity when applying.Employed food is the water cleaning easily.
The present invention describes in more detail with reference to following non-restrictive example.
Embodiment:
I. synthesizing of highly branched polymkeric substance
HBP 1: hyperbranched polycarbonates
The flask of a 4L is equipped with agitator, gas inlet pipe, internal thermometer and reflux exchanger, to wherein adding the trivalent alcohol that 1417.6g diethyl carbonate, the 2400.0g propoxylation by the TriMethylolPropane(TMP) that on average contains 1.5 propylene oxide units obtains, and 0.4g salt of wormwood, with this initial charge under atmospheric pressure, follow gentle nitrogen to feed and be heated to about 130 ℃.In the process of polycondensation, owing to generate as the alcoholic acid of condensation product, the temperature of reaction mixture is reduced to 105 ℃ in the process of 4h.During in boiling temperature, reflux exchanger is distilled device and replaces when constant, and this water distilling apparatus is made up of the filling post of 20cm, a descending condenser and a receiving vessel, and ethanol is steamed continuously.When removing the 770g overhead product, reaction mixture is cooled to 100 ℃, and is that 85% phosphoric acid neutralizes salt of wormwood by adding 0.5g concentration.Mixture is stirred above 1h down at 100 ℃.Carry under 140 ℃ with nitrogen then and heat up in a steamer about 0.5h, the residuum of volatile constituent is removed during this period.Afterwards, cooling and assay products.Hydroxyl value is 421mg KOH/g; (eluent=DMAC, demarcation=PMMA) definite molecular weight is M by GPC n=980g/mol and M w=1450g/mol.
HBP 2: hyperbranched polycarbonates
The flask of a 4L is equipped with agitator, gas inlet pipe, internal thermometer and reflux exchanger, to wherein adding the trivalent alcohol that 591g diethyl carbonate, the 3350g propoxylation by the TriMethylolPropane(TMP) that on average contains 12 propylene oxide units obtains, and 0.5g potassium hydroxide, with this initial charge under atmospheric pressure, follow gentle nitrogen to feed and be heated to about 140 ℃.In the process of polycondensation, owing to generate as the alcoholic acid of condensation product, the temperature of reaction mixture is reduced to 110 ℃ in the process of 4h.During in boiling temperature, reflux exchanger is distilled device and replaces when constant, and this water distilling apparatus is made up of the filling post of 20cm, a descending condenser and a receiving vessel, and ethanol is steamed continuously.When removing the 405g overhead product, reaction mixture is cooled to 100 ℃, and is that 85% phosphoric acid neutralizes potassium hydroxide by adding 0.5g concentration.Mixture is stirred above 1h down at 100 ℃.Carry under 140 ℃ with nitrogen then and heat up in a steamer about 0.5h, the residuum of volatile constituent is removed during this period.Afterwards, cooling and assay products.Hydroxyl value is 151mg KOH/g; (eluent=DMAC, demarcation=PMMA) definite molecular weight is M by GPC n=2750g/mol and M w=5700g/mol.
HBP 3: hyperbranched polycarbonates
The flask of a 4L is equipped with agitator, gas inlet pipe, internal thermometer and reflux exchanger, to wherein adding the trivalent alcohol that 1182g diethyl carbonate, the 2750g propoxylation by the TriMethylolPropane(TMP) that on average contains 3 propylene oxide units obtains, and 0.4g salt of wormwood, with this initial charge under atmospheric pressure, follow gentle nitrogen to feed and be heated to about 140 ℃.In the process of polycondensation, owing to generate as the alcoholic acid of condensation product, the temperature of reaction mixture is reduced to 110 ℃ in the process of 4h.During in boiling temperature, reflux exchanger is distilled device and replaces when constant, and this water distilling apparatus is made up of the filling post of 20cm, a descending condenser and a receiving vessel, and ethanol is steamed continuously.When removing the 828g overhead product, reaction mixture is cooled to 100 ℃, and is that 85% phosphoric acid neutralizes salt of wormwood by adding 0.5g concentration.Mixture is stirred above 1h down at 100 ℃.Carry under 140 ℃ with nitrogen then and heat up in a steamer about 0.5h, the residuum of volatile constituent is removed during this period.Afterwards, cooling and assay products.Hydroxyl value is 274mg KOH/g; (eluent=DMAC, demarcation=PMMA) definite molecular weight is M by GPC n=2170g/mol and M w=5400g/mol.
II. the preparation of polymeric dispersions
Embodiment 1: the preparation of dispersion 1
To one the following material of adding in measuring apparatus and the thermostatic polymerization container is installed:
Initial charge:
528.0g water
46.7g solids content be 33% and median size be the polystyrene kind dispersion of 30nm
3.67g concentration is the aqueous solution of 15% Sodium Lauryl Sulphate BP/USP
Afterwards, this initial charge under agitation is heated to 85 ℃.Subsequently, remain under this temperature, with material 2 addings of 5 weight %, and with mixture stirring 5 minutes.Afterwards material 1 was metered in 180 minutes, remaining material 2 added in 195 minutes simultaneously.
Material 1:
543.2g water
125.4g the aqueous solution of the Sodium Lauryl Sulphate BP/USP of concentration 15%
458.0g n-butyl acrylate
399.6g methyl methacrylate
165.1g vinylbenzene
22.78g methacrylic acid
21.45g methacrylic acid urea ester (N-(2-methacryloxyethyl) tetrahydroglyoxaline-2-ketone)
33.0g Bisomer MPEG 350MA (available from the methoxy poly (ethylene glycol) monomethacrylates of Laporte PerformanceChemicals UK)
Material 2:
83.6g water
4.4g peroxidation sodium pyrosulfate
After the adding of material 1 finishes, add 22g water; After the adding of material 2 finishes, polymerization was continued 30 minutes, and make the batch of material neutralization with 7.47g ammoniacal liquor (concentration is 25% the aqueous solution).Afterwards 13.2g hydrogen peroxide (concentration is 5% the aqueous solution) is added, the solution that the 0.557g xitix is dissolved in 4.96g water was metered in 60 minutes.Afterwards, make dispersion cool off and pass through the strainer filtration of 125 μ m.Generate 2.48kg concentration thus and be 46% dispersion.
Hyperbranched polymer HBP 1 and HBP 2 are sneaked in the dispersion 1 with the pure substance form, and it is measured as shown in Tables 3 and 4.
Embodiment 2: the preparation of dispersion 2
To one the following material of adding in measuring apparatus and the thermostatic polymerization container is installed:
584.0g water
56.9g solids content be 33% and median size be the polystyrene kind dispersion of 30nm
4.47g concentration is the aqueous solution of 15% Sodium Lauryl Sulphate BP/USP
Afterwards, this initial charge under agitation is heated to 85 ℃.Subsequently, remain under this temperature, with material 2 addings of 5 weight %, and with mixture stirring 5 minutes.Afterwards material 1 was metered in 180 minutes, remaining material 2 added in 195 minutes simultaneously.
Material 1:
595.6g water
153.0g the aqueous solution of the Sodium Lauryl Sulphate BP/USP of concentration 15%
576.3g n-butyl acrylate
529.6g methyl methacrylate
207.6g vinylbenzene
28.59g methacrylic acid
Material 2:
16.1g concentration is the aqueous solution of 5% peroxidation sodium pyrosulfate
After the adding of material 1 finishes, add 27g water; After the adding of material 2 finishes, polymerization was continued 30 minutes, and make the batch of material neutralization with 9.13g ammoniacal liquor (concentration is 25% the aqueous solution).Afterwards 16.11g hydrogen peroxide (concentration is 5% the aqueous solution) being added, is that 10% aqueous ascorbic acid was metered in 60 minutes with 6.71g concentration.Afterwards, make dispersion cool off and pass through the strainer filtration of 125 μ m.Generate 2.85kg concentration thus and be 48% dispersion.
Hyperbranched polymer HBP 3 is sneaked in the dispersion 1 with the pure substance form, and its amount is as shown in table 5.
III. performance embodiment
1. the preparation of water-miscible paint
Each component (manufacturers sees Table 1) is metered into amount shown in the table 2 (weight part) and order under the stirring of using toothed disk stirrer.After adding TiO 2 pigment, speed is increased to 2000rpm, and it is level and smooth until pigment paste that batch of material is disperseed, and promptly do not contain piece.Then, if desired, it is cooled to room temperature, under the speed that reduces, adds remaining ingredient.The preparation tackiness agent that is used for water-borne coatings shown in the table 2 does not contain highly branched or hyperbranched polymers.For the coating that contains hyperbranched polymer of the present invention, the weight content of corresponding tackiness agent raises, and corresponding thus minimizing water-content compensates.
Table 1
Figure GPA00001139222000611
Table 2: the prescription of water-borne coatings
2. the test of water-miscible paint (coating)
The glossiness of coating is determined according to DIN EN ISO 2813: is that 240 μ m are coated on the plate of coming off duty with coating to stitch wide, and at room temperature dry 72 hours.Sample is inserted mist degree-gloss reflexometer through calibration, and (Byk-Gardner Geretsried), reads the value of reflexometer 20 ° of input angles and 60 °, and mist degree (haze).The value of determined reflexometer is that of glossiness measures (this value is high more, and glossiness is high more).
Table 3: hyperbranched polymer HBP1 is added in the acrylate dispersoid 1:
Figure GPA00001139222000621
*Based on dispersion solid weight percent
Table 4: in acrylate dispersoid 1, add hyperbranched polymer HBP 2
Figure GPA00001139222000622
*Based on dispersion solid weight percent
Along with the content increase of hyperbranched polymer, glossiness increases, and mist degree reduces.
Table 5: in acrylate dispersoid 2, add hyperbranched polymer HBP 3
Figure GPA00001139222000623

Claims (27)

1. method for preparing the coating of glossiness with increase, it is by a kind of water-borne coatings of coating in substrate, described water-borne coatings contains a kind of aqueous polymer dispersions PD) and a kind of highly-branched polymers.
2. the process of claim 1 wherein and be applied to described suprabasil described water-borne coatings and contain a kind of aqueous polymer dispersions PD that comprises described highly-branched polymers as additive).
3. claim 1 or 2 method, wherein said highly-branched polymers is at least a hyperbranched polymer.
4. the method for claim 3, wherein said hyperbranched polymer have 10% to 95%, preferred 25% to 90%, more preferably 30% to 80% degree of branching DB.
5. each method during aforesaid right requires, wherein said highly-branched polymers are selected from polycarbonate, polyester, polyethers, polyurethane(s), polyureas, polyamine, polymeric amide poly-(Semicarbazido manthanoate), poly-(ester amine), poly-(ether amine), poly-(esteramides), poly-(amido amine), poly-(ester carbonic ether), poly-(ether carbonate), poly-(ether-ether), poly-(ether-ether carbonic ether) and composition thereof.
6. each method among the claim 1-5, wherein said highly-branched polymers is hyperbranched polycarbonate, poly-(ether carbonate), poly-(ester carbonic ether) or poly-(ether-ether carbonic ether), or contains the mixture of at least a hyperbranched polymer in hyperbranched polycarbonate, poly-(ether carbonate), poly-(the ester carbonic ether) or poly-(ether-ether carbonic ether).
7. each method among the claim 1-5, wherein said hyperbranched polymer is A 2B xForm, preferred A 2B 3The hyper-branched polyester of form.
8. each method during aforesaid right requires, wherein said polymeric dispersions PD) contain at least a highly-branched polymers of 0.1 weight % to 15 weight %, preferred 0.5 weight % to 10 weight %, based on the gross weight meter of described polymeric dispersions.
9. each method during aforesaid right requires, wherein said aqueous polymer dispersions PD) can be by at least a ethylenically unsaturated monomers M) free-radical emulsion polymerization obtain.
10. the method for claim 9, wherein said monomer M) be selected from α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 1-C 20The ester of alkanol, vinyl aromatic compounds, vinyl alcohol and C 1-C 30The ester of monocarboxylic acid, ethylenic unsaturated nitrile, vinyl halide, vinylidene halogen, single ethylenic unsaturated carboxylic acid and sulfonic acid, phosphorus monomer, α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 2-C 30The ester of alkane glycol, α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and contain primary amino or the C of secondary amino group 2-C 30The acid amides of amino alcohol, α, the primary amide of β-ethylenic unsaturated monocarboxylic and N-alkyl derivative and N, N-dialkyl derivatives, N-vinyl lactam, open chain N-vinylamide compound, vinyl carbinol and C 1-C 30The ester of monocarboxylic acid, α, ester, the α of β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and amino alcohol, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and contain primary amino or secondary amino group in acid amides, the N of at least a diamines, N-diallyl amine, N, the nitrogen heterocyclic, vinyl ether, the C that replace with allyl group of N-diallyl-N-alkylamine, vinyl substituted 2-C 8Monoolefine, the non-aromatic hydrocarbon with at least two conjugation both shoulders, polyethers (methyl) acrylate, contain the monomer of urea groups and the mixture of above-mentioned substance.
11. the method for claim 9 or 10, wherein at least 40 weight %, preferred at least 60 weight %, the more preferably at least a monomer M 1 of at least 80 weight % are used in letex polymerization) carry out, described amount is based on monomer M) the gross weight meter, described monomer M 1) is selected from α, β-ethylenic unsaturated monocarboxylic and dicarboxylic acid and C 1-C 20The ester of alkanol, vinyl aromatic compounds, vinyl alcohol and C 1-C 30The ester of monocarboxylic acid, ethylenic unsaturated nitrile, vinyl halide, vinylidene halogen, and the mixture of above-mentioned substance.
12. the method for claim 11, wherein maximum 60 weight %, preferred maximum 40 weight %, the more preferably at least a monomer M 2 of maximum 20 weight % are also used in letex polymerization) carry out, described amount is based on monomer M) the gross weight meter, described monomer M 2) be selected from the acid anhydrides of ethylenic unsaturated monocarboxylic and dicarboxylic acid and ethylenic unsaturated dicarboxylic acid and monoesters, (methyl) acrylamide, (methyl) vinylformic acid C 1-C 10Hydroxy alkyl ester, C 1-C 10Hydroxyalkyl (methyl) acrylamide, and the mixture of above-mentioned substance.
13. the method for claim 11 or 12, wherein letex polymerization also uses at least a polyethers (methyl) acrylate of maximum 25 weight %, preferred maximum 20 weight % to carry out, and described amount is based on monomer M) the gross weight meter.
14. the method for claim 13, wherein said polyethers (methyl) acrylate is selected from compound or its mixture of general formula I or II
Figure FPA00001139221900021
Wherein
N is 3 to 15, preferred 4 to 12 integer,
R aBe hydrogen, C 1-C 20Alkyl, C 5-C 8Cycloalkyl or C 6-C 14Aryl
R bBe hydrogen or methyl.
15. each method among the claim 11-14, wherein letex polymerization also uses at least a monomer that contains urea groups of maximum 25 weight %, preferred maximum 20 weight % to carry out, and described amount is based on monomer M) the gross weight meter.
16. the coating of a waterborne compositions form, it comprises:
The dispersion PD of each definition among the-at least a claim 11-14), it comprises a kind of highly-branched polymers as additive,
-optional at least a mineral filler and/or at least a mineral dye,
-optional conventional auxiliary agent and
-water.
17. the coating of claim 16, it is the form of transparent varnish.
18. the coating of claim 16, it is the form of emulsion paint.
19. the coating of claim 18, it comprises:
At least a dispersion PD that comprises a kind of highly-branched polymers as additive of-10 weight % to 60 weight %),
Mineral filler and/or the mineral dye of-10 weight % to 70 weight %,
The conventional auxiliary agent of-0.1 weight % to 20 weight % and
-add to the water of 100 weight %.
20. the coating of claim 18 or 19, it is the form of water-based semi-gloss paint or high gloss paint.
21. each coating among the claim 18-20, its be glossiness when 20 ° of input angles greater than 60 high gloss paint.
22. each coating among the claim 18-21, its be glossiness when 60 ° of input angles greater than 80 high gloss paint.
23. each coating among the claim 18-22, its be PVC in 12 to 35 scope, the preferred high gloss paint in 15 to 30 scope.
24. each highly-branched polymers is used to increase the purposes of the glossiness of the coating that is generated by this coating as the additive of water-borne coatings among the claim 1-7, described water-borne coatings contains a kind of aqueous polymer dispersions PD).
25. contain the aqueous polymer dispersions PD of the highly-branched polymers of each definition among the claim 1-7) as the purposes of the binder component of high gloss paint.
26. at least a highly-branched polymers is used to increase the purposes of the glossiness of the coating that is generated by this coating as the additive of coating, described coating contains a kind of α based on each definition among at least a claim 9-15, β-ethylenically unsaturated monomers M) emulsion polymer.
27. the purposes of claim 26 is as the additive of lacquer.
CN200880116779.6A 2007-11-19 2008-11-19 Use of highly branched polymers in polymer dispersions for gloss colours Expired - Fee Related CN101868509B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
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